CN107073867B - Stacking pipe - Google Patents

Stacking pipe Download PDF

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Publication number
CN107073867B
CN107073867B CN201580049013.0A CN201580049013A CN107073867B CN 107073867 B CN107073867 B CN 107073867B CN 201580049013 A CN201580049013 A CN 201580049013A CN 107073867 B CN107073867 B CN 107073867B
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China
Prior art keywords
polyamide
composition
layer
poly
mass
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CN201580049013.0A
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Chinese (zh)
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CN107073867A (en
Inventor
中村孝治
安部武尊
藤井广昭
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Ube Corp
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Ube Industries Ltd
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Classifications

    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
    • F16L11/00—Hoses, i.e. flexible pipes
    • F16L11/04—Hoses, i.e. flexible pipes made of rubber or flexible plastics
    • F16L11/045—Hoses, i.e. flexible pipes made of rubber or flexible plastics with four or more layers without reinforcement
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/09—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
    • B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
    • B29C48/21—Articles comprising two or more components, e.g. co-extruded layers the components being layers the layers being joined at their surfaces
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B1/00—Layered products having a non-planar shape
    • B32B1/08—Tubular products
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/22—Layered products comprising a layer of synthetic resin characterised by the use of special additives using plasticisers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/15—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state
    • B32B37/153—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state at least one layer is extruded and immediately laminated while in semi-molten state
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60K—ARRANGEMENT OR MOUNTING OF PROPULSION UNITS OR OF TRANSMISSIONS IN VEHICLES; ARRANGEMENT OR MOUNTING OF PLURAL DIVERSE PRIME-MOVERS IN VEHICLES; AUXILIARY DRIVES FOR VEHICLES; INSTRUMENTATION OR DASHBOARDS FOR VEHICLES; ARRANGEMENTS IN CONNECTION WITH COOLING, AIR INTAKE, GAS EXHAUST OR FUEL SUPPLY OF PROPULSION UNITS IN VEHICLES
    • B60K15/00—Arrangement in connection with fuel supply of combustion engines or other fuel consuming energy converters, e.g. fuel cells; Mounting or construction of fuel tanks
    • B60K15/01—Arrangement of fuel conduits
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02M—SUPPLYING COMBUSTION ENGINES IN GENERAL WITH COMBUSTIBLE MIXTURES OR CONSTITUENTS THEREOF
    • F02M37/00—Apparatus or systems for feeding liquid fuel from storage containers to carburettors or fuel-injection apparatus; Arrangements for purifying liquid fuel specially adapted for, or arranged on, internal-combustion engines
    • F02M37/0011—Constructional details; Manufacturing or assembly of elements of fuel systems; Materials therefor
    • F02M37/0017—Constructional details; Manufacturing or assembly of elements of fuel systems; Materials therefor related to fuel pipes or their connections, e.g. joints or sealings
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
    • F16L11/00—Hoses, i.e. flexible pipes
    • F16L11/04—Hoses, i.e. flexible pipes made of rubber or flexible plastics
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
    • B29K2023/04—Polymers of ethylene
    • B29K2023/08—Copolymers of ethylene
    • B29K2023/083—EVA, i.e. ethylene vinyl acetate copolymer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2079/00—Use of polymers having nitrogen, with or without oxygen or carbon only, in the main chain, not provided for in groups B29K2061/00 - B29K2077/00, as moulding material
    • B29K2079/08—PI, i.e. polyimides or derivatives thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2023/00—Tubular articles
    • B29L2023/22—Tubes or pipes, i.e. rigid
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/04—4 layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/05—5 or more layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/24—All layers being polymeric
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/202—Conductive
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/546—Flexural strength; Flexion stiffness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/726—Permeability to liquids, absorption
    • B32B2307/7265—Non-permeable
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2439/00—Containers; Receptacles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2597/00—Tubular articles, e.g. hoses, pipes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2605/00—Vehicles
    • B32B2605/08—Cars

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Transportation (AREA)
  • Rigid Pipes And Flexible Pipes (AREA)
  • Laminated Bodies (AREA)

Abstract

A kind of stacking pipe is provided, with following layers: including the layer of fatty polyamide (polyamide 11,12 etc.)；Include polyamide 6 composition, polyamide 6/66/12 composition layer；Include the saponified layer of ethylene/vinyl acetate；And the layer comprising semiaromatic polyamide composition composition, the semiaromatic polyamide composition composition include the semiaromatic polyamide composition with specific structure.Also, a kind of stacking pipe is provided, is also had containing fluorine system polymer, described imported in strand containing fluorine system polymer has reactive functional group to amino.

Description

Stacking pipe
Technical field
The present invention relates to stackings to manage.
Background technique
For automobile piping Guan Eryan, all the time for the antifreezing agent because of road caused by problem of rustiness, prevent Global warming, the requirement of energy-saving, main raw material(s) gradually by metal substitute at rust-preventing characteristic excellent and light weight resin.It is logical Polyamide resin, saturated polyester system resin, polyolefin-based resins, thermoplasticity can be enumerated by being often used as the resin with effective pipe Polyurethane series resin etc., but in the case where mono-layer tube obtained from using them, no due to heat resistance, chemical reagent resistance etc. Sufficiently, therefore its applicable is limited in scope.
In addition, conveying, which is blended, in automobile piping pipe first from the viewpoint of the consumption of saving gasoline, high performance The oxygenated gasoline etc. of the ethers such as the low boiling points such as alcohol, ethyl alcohol alcohols or ethyl tert-butyl ether (ETBE) (ETBE).In turn, from preventing environment From the perspective of pollution, stringent gas emission regulation below is implemented, which includes preventing from having passed through separating with effective pipe Volatile hydrocarbon of wall etc. is revealed by spreading into atmosphere.For the strict regulations, being used alone for using in the past is poly- The excellent polyamide 11 of amide system resin, especially intensity, toughness, chemical reagent resistance, flexibility etc. or polyamide 12 and obtain The mono-layer tube arrived is insufficient to the anti-permeability of afore mentioned chemical solution, especially requires changing for anti-alcohol blended fuel permeability It is good.
As a solution to the problem, it proposes configured with the anti-good resin of chemical solution permeability, such as ethylene/ Vinyl acetate copolymer saponified (EVOH), poly-meta-xylylene adipamide (polyamide MXD6), poly terephthalic acid fourth two Alcohol ester (PBT), polybutylene naphthalate (PBN), polyphenylene sulfide (PPS), gathers partially at polyethylene naphthalate (PEN) Difluoroethylene (PVDF), Tefzel (ETFE), ethylene/tetrafluoroethylene/hexafluoropropylene copolymer (EFEP), Ethylene/chlorotrifluoroethylene (ECTFE), tetrafluoroethylene/hexafluoropropylene copolymer (TFE/HFP, FEP), tetrafluoroethene/six Fluoropropene/vinylidene fluoride copolymer (TFE/HFP/VDF, THV), tetrafluoroethylene/hexafluoropropylene/vinylidene fluoride/perfluor (alkane Base vinyl ethers) copolymer (TFE/HFP/VDF/PAVE), tetrafluoroethylene/perfluoro (alkyl vinyl ether) copolymer (TFE/ PAVE, PFA), tetrafluoroethylene/hexafluoropropylene/perfluor (alkyl vinyl ether) copolymer (TFE/HFP/PAVE), trifluoro chloroethene Alkene/perfluor (alkyl vinyl ether)/TFE copolymer (CTFE/PAVE/TFE, CPT) stacking pipe is (referring for example to the U.S. No. 5554425 specification of patent etc.).
It is the anti-chemical solution permeability of ethylene/vinyl acetate saponified (EVOH), especially right among these The anti-permeability of gasoline is very excellent.For example, proposing the fuel distribution tube being made of following layer: being formed most by polyamide 12 Outer layer, the outer layer formed by polyamide 6, is saponified by ethylene/vinyl acetate the adhesive layer formed by improved polyalkene The middle layer of object (EVOH) formation, the innermost layer formed by polyamide 6 (referring for example to Japanese Unexamined Patent Publication 3-177683 bulletin). However, when using polyamide 6 in the piping as innermost layer, the patience of sour gasoline for being acidified and generating to gasoline is (resistance to Deteriorate fuel), it is poor to the patience (chemical reagent resistance) of calcium chloride.Further it is proposed that being answered by the stacking that following layer is constituted Close object: the outermost layer that is formed by polyamide 12, by selected from by polyamide 6/12 copolymers, 12/6 copolymer of polyamide, polyamide 612, at least one kind of formation in the group of the mixture of polyamide 610, polyamide 12 and polyamide 6 and compatibility agent composition is viscous It connects layer, the middle layer formed by ethylene/vinyl acetate saponified (EVOH), formed by polyamide 6 or polyamide 12 Innermost layer (referring for example to Japanese Unexamined Patent Application Publication 2003-535717 bulletin, Japanese Unexamined Patent Publication 2003-021276 bulletin).Similarly, Propose the stacking compound being made of following layer: the outermost layer that is formed by polyamide 12, by polyamide 6 and polyamide 12 with The adhesive layer of polyamines/polyamide copolymer mixture formation is formed by ethylene/vinyl acetate saponified (EVOH) Middle layer, the innermost layer that is formed by polyamide 6 or polyamide 12 (referring for example to Japanese Unexamined Patent Publication 2002-210904 bulletin). In the technology, as the adhesive layer between polyamide 12 and the saponified the two of ethylene/vinyl acetate, propose The polyamide copolymer of specific composition ratio, the mixture comprising polyamide 6 and polyamide 12 and phase solvation be used as have it is good The material of good layers cementing intensity.
In turn, it proposes in internal layer configured with fluorine resin, in the outside relative to it configured with Ethylene/vinyl acetate Copolymer saponated material and outer layer configured with polyterephthalamide (PPA) stacking pipe (referring for example to United States Patent (USP) 2010- No. 0035116 specification).
Existing technical literature
Patent document
Patent document 1: No. 5554425 specifications of U.S. Patent No.
Patent document 2: Japanese Unexamined Patent Publication 3-177683 bulletin
Patent document 3: Japanese Unexamined Patent Application Publication 2003-535717 bulletin
Patent document 4: Japanese Unexamined Patent Publication 2003-021276 bulletin
Patent document 5: Japanese Unexamined Patent Publication 2002-210904 bulletin
Patent document 6: United States Patent (USP) 2010-0035116 specification
Summary of the invention
Problems to be solved by the invention
However, when using polyamide 6 as innermost layer, not yet solution resistant to deterioration is fuel, resistance to zinc chloride, resistance to calcium chloride The project of property equal difference.In turn, when polyamide 12 being used for the innermost layer of fuel distribution tube, and being contacted with fuel such as alcohol blended fuels The dissolution such as the low molecular weight compositions such as monomer, oligomer, additive, plasticizer is caused to be precipitated into alcohol blended fuel, and at normal temperature. Thus, worry the blocking in the fuel distribution tubes such as automobile piping pipe, filter, nozzle.
In addition, in aforementioned stacking pipe, in the layer formed by fatty polyamide and by ethylene/vinyl acetate soap It is formed between the layer that compound (EVOH) is formed by polyamide 6/12 copolymers, 12/6 copolymer of polyamide, polyamide 612, gathered The adhesive layer of the formation such as the mixture of amide 610, polyamide 12 and polyamide 6 and compatibility agent, initial adhesiveness between layers are Adequately.On the other hand, these stacking pipes due to design on restriction, collision when deformation absorb etc., be usually processed into and applying Add the pipe in the state of bending stress with intended shape.At this point, for ease of hot-working, in the glass transition of constituent material It is more than temperature~fusing point below range in by Guan Jiare, still, if heat treatment after do not have sufficient adhesiveness between layers, can The case where innermost layer is removed and caused with blockage when generating insertion connector, outermost layer are removed and lose resistance to pressure, yield strength The problem of Deng original performance as pipe.Therefore, it for the adhesiveness between layers (durabilities of adhesiveness between layers) after heat treatment, deposits In room for improvement.
In turn, with ethylene/vinyl acetate saponified (EVOH) although stacking pipe to containing low concentration alcohol The anti-through performance of gasoline is excellent, still, insufficient to the anti-through performance of the gasoline of the alcohol containing high concentration, it is therefore desirable for further Improve.As the means for solving them, proposes in United States Patent (USP) 2010-0035116 specification and configured in internal layer Have fluorine resin, it is saponified configured with ethylene/vinyl acetate in the outside relative to it and in outer layer configured with poly- The stacking pipe of terephthalamide (PPA).However, the pipe of adhesiveness between layers, low-temperature impact resistance etc is directed in the document Basic performance, disclosure, technical inspiration without particular technique data.
It is an object of the present invention to solve problem point, anti-chemical solution permeability, adhesiveness between layers and its resistance to are provided The stacking pipe that long property, low-temperature impact resistance, resistant to deterioration are fuel and resistance to monomer, oligomer stripping property are excellent.
The solution to the problem
The inventors of the present invention have made intensive studies to solve problem point, as a result, it has been found that: there is fatty adoption The layer of amide (polyamide 11,12 etc.) contains polyamide 6 composition, polyamide 6/layer of 66/12 composition, second containing ethylene/acetic acid The stacking pipe of the saponified layer of enoate copolymer and the layer containing the semiaromatic polyamide composition composition with specific structure resists Chemical solution permeability, adhesiveness between layers and its durability, low-temperature impact resistance, resistant to deterioration be fuel, resistance to monomer, oligomer are molten Each excellent such as property out.
That is, an embodiment of the invention is a kind of stacking pipe, it is with (a) layer, (b) layer, (c) layer and (d) layer And the stacking pipe at least formed by 4 layers,
Aforementioned (a) layer includes fatty polyamide (A),
Aforementioned (b) layer includes polyamide 6 composition (B1) and/or polyamide 6/66/12 composition (B2),
Aforementioned (c) layer includes that ethylene/vinyl acetate is saponified (C),
Aforementioned (d) layer includes semiaromatic polyamide composition composition (D1) or semiaromatic polyamide composition composition (D2),
Aforementioned fatty polyamide (A) is free of polycaprolactam (polyamide 6) and poly- (caproamide/hexamethylene adipamide/12 Alkane amide) (polyamide 6/66/12),
6 composition of foregoing polyamides (B1) containing polycaprolactam (polyamide 6) 50 mass % or more and 98 mass % or less, 1 mass % of plasticizer (B3) or more and 20 mass % or less and according to ISO 178 measure bending elastic modulus be 500MPa 1 mass % of olefin polymer (B4) or more below and 30 mass % hereinafter,
6/66/12 composition of foregoing polyamides (B2) containing 50 mass % of polyamide compound or more and 98 mass % with Under, 1 mass % of plasticizer (B3) or more and 20 mass % or less and according to the bending elastic modulus that ISO 178 is measured be 1 mass % of 500MPa olefin polymer below (B4) or more and 30 mass % are hereinafter, the polyamide compound includes polyamides Amine 6/66/12 and selected from by polyhexamethylene sebacamide (polyamide 610), nylon 612 (polyamide 612), the poly- last of the ten Heavenly stems Two acyl nonamethylene diamines (polyamide 910), two acyl nonamethylene diamine (polyamide 912) of poly- dodecane, nylon 1010 (polyamide 1010), the group of poly- two acyl decamethylene diamine (polyamide 1012) of dodecane and two acyl lauryl amine (polyamide 1212) of poly- dodecane composition In at least one kind of polyamide,
Aforementioned semiaromatic polyamide composition composition (D1) includes semiaromatic polyamide composition (d1), aforementioned semiaromatic polyamide composition (d1) there are diamine unit and dicarboxylic acid units, it is 50 moles of % or more that the diamine unit, which includes relative to whole diamine units, , the aliphatic diamine unit below of carbon number 9 or more and 13, the dicarboxylic acid units include to be relative to whole dicarboxylic acid units The terephthalic acid units and/or naphthalenedicarboxylic acid unit of 50 moles of % or more, aforementioned semi-aromatic composition (D2) include half virtue Fragrant polyamide (d2), aforementioned semiaromatic polyamide composition (d2) have diamine unit and dicarboxylic acid units, the diamine unit packet It is described containing the benzene dimethylamine unit and/or bis- (amino methyl) naphthalene units for being 50 moles of % or more relative to whole diamine units It is 50 moles of % or more, the aliphatic below of carbon number 8 or more and 13 that dicarboxylic acid units, which include relative to whole dicarboxylic acid units, Dicarboxylic acid units.
The preferred embodiment of stacking pipe described below.Preferred mode can be combined a variety of.
[1] a kind of stacking pipe, wherein fatty polyamide (A) is selected from by poly- undecanoic amide (polyamide 11), poly- ten Dioxane amide (polyamide 12), polyhexamethylene adipamide (polyamide 66), polyhexamethylene sebacamide (polyamide 610), poly- 12 Two acyl hexamethylene diamine (polyamide 612) of alkane, nylon 1010 (polyamide 1010), two acyl decamethylene diamine (polyamide of poly- dodecane 1012) and poly- two acyl lauryl amine (polyamide 1212) of dodecane composition group at least one kind of homopolymer, and/or use Copolymer obtained from a variety of starting monomers for forming these polyamide.
[2] a kind of stacking pipe, wherein in polyamide 6/66/12 in polyamide 6/66/12 composition (B2), relative to Total 100 mass % of hexanoyl amine unit, hexamethyleneadipamide unit and dodecanoyl amine unit, hexanoyl amine unit and adipyl The total unit of hexamethylene diamine unit and the mass ratio of dodecanoyl amine unit are 81 mass %:19 mass % or more and 95 matter Measure %:5 mass % or less.
[3] a kind of stacking pipe, wherein the ethylene contents of ethylene/vinyl acetate saponified (C) are 15 moles of % Above and 60 moles of % or less, saponification degree are 90 moles of % or more.
[4] a kind of stacking pipe, wherein (a) layer is configured in outermost layer, and (c) layer is configured in (a) layer and (d) between layer.
[5] a kind of stacking pipe, wherein configuring (b) layer with the adjacent at least side of (c) layer.
[6] a kind of stacking pipe, wherein configure conductive layer in the innermost layer of stacking pipe, the conductive layer includes containing conduction The semiaromatic polyamide composition composition (D) of property filler.
[7] a kind of stacking pipe also has (e) layer, and aforementioned (e) layer includes (E) containing fluorine system polymer, described poly- containing fluorine system Closing object (E) and having imported in strand has reactive functional group to amino.
[8] a kind of stacking pipe, wherein (a) layer is configured in outermost layer, (c) layer and (d) layer is configured in (a) layer and (e) Between layer.
[9] a kind of stacking pipe, wherein configure conductive layer in the innermost layer of stacking pipe, the conductive layer includes containing conduction The fluorine-containing based polymer composition of property filler.
[10] a kind of stacking pipe, is manufactured by coextrusion forming process.
[11] a kind of stacking pipe, is used as cartridge.
The effect of invention
In accordance with the invention it is possible to provide anti-chemical solution permeability, adhesiveness between layers and its durability, low temperature impact The stacking pipe that property, resistant to deterioration are fuel and resistance to monomer, oligomer stripping property are excellent.
Specific embodiment
In this specification, when there is a variety of substances being consistent with each ingredient in the composition, each ingredient in composition Amount refers to the total amount of many kinds of substance present in composition in case of no particular description.
Described in present embodiment stacking pipe by with the layer comprising fatty polyamide, comprising polyamide 6 composition, Polyamide 6/66/12 composition layer, comprising the saponified layer of ethylene/vinyl acetate and comprising with specific The layer of the semiaromatic polyamide composition composition of the semiaromatic polyamide composition of structure, to take into account adhesiveness between layers and anti-chemical solution Permeability, and each excellent such as low-temperature impact resistance, resistant to deterioration are fuel, resistance to monomer, oligomer stripping property.Especially, energy Enough alcohol hydrocarbon mixtures for inhibiting to evapotranspire from the partition wall of pipe transmission, and meet stringent environment regulations, therefore be suitable as fuel Pipe.In turn, after contacting/being impregnated in fuel for a long time, after heat treatment etc., the reduction of layers cementing power is few, adhesiveness between layers Excellent in te pins of durability.Thus, stacking pipe described in present embodiment can use under all circumstances, and high reliablity, utilize Value is very big.
(1. a) layer
(a) layer that pipe is laminated includes fatty polyamide (A).
[fatty polyamide (A)]
Fatty polyamide (A) has amido bond (- CONH-) in main chain, by belong to fatty polyamide structure Lactams, amino carboxylic acid or the aliphatic diamine and aliphatic dicarboxylic acid of unit utilize melt polymerization, solution as raw material Method well known to polymerization, solid phase etc. is polymerize or is copolymerized to obtain.But fatty polyamide (A) is free of poly- hexanoyl Amine (polyamide 6) and poly- (caproamide/hexamethylene adipamide/dodecane amide) (polyamide 6/66/12).
As lactams, oenantholcatam, 11 lactams, lauric lactam, alpha-pyrrolidone, α-piperidones can be enumerated Deng.As amino carboxylic acid, 7- aminoheptylic acid, 9 aminononanoic acid, 11- amino undecanoic acid, 12 amino dodecanoic acid can be enumerated Deng.They can be used one kind or two or more.
As aliphatic diamine, 1,2- ethylenediamine, 1,3- propane diamine, Putriscine, 1,5- pentanediamine, 1 can be enumerated, 6- hexamethylene diamine, 1,7- heptamethylene diamine, 1,8- octamethylenediamine, 1,9-nonamethylene diamine, 1,10- decamethylene diamine, 1,11- hendecane diamines, 1,12- ten Dioxane diamines, 1,13- tridecane diamine, 1,14- tetradecane diamines, 1,15- pentadecane diamines, 1,16- hexadecane diamines, 1, 17- heptadecane diamines, 1,18- octadecamethylene diamine, 1,19- nonadecane diamines, 1,20- eicosane diamines, 2- methyl-1,5- penta 2 Amine, 3- methyl-1,5- pentanediamine, 2- methyl-1,8- octamethylenediamine, 2,2,4- trimethyl -1,6- hexamethylene diamine, 2,4,4- trimethyl - 1,6- hexamethylene diamine, 5- methyl-1,9- nonamethylene diamine etc..They can be used one kind or two or more.
As aliphatic dicarboxylic acid, ethanedioic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, pungent can be enumerated Diacid, azelaic acid, decanedioic acid, heneicosanedioic acid, dodecanedioic acid, tridecandioic acid, tetracosandioic acid, pentacosandioic acid, ten Six docosandioic acids, octadecane diacid, eicosane diacid etc..They can be used one kind or two or more.
As fatty polyamide (A), poly- undecanoic amide (polyamide 11), poly- dodecane amide (polyamides can be enumerated Amine 12), poly hexamethylene adipamide ethylenediamine (polyamide 26), polybutadiene acyl butanediamine (polyamide 44), poly- glutaryl butanediamine (polyamide 45), nylon 46 (polyamide 46), poly- suberoyl butanediamine (polyamide 48), polytetramethylene azelamide (polyamide 49), polytetramethylene sebacamide (polyamide 410), two acyl butanediamine (polyamide 412) of poly- dodecane, polybutadiene acyl pentanediamine are (poly- Amide 54), poly- glutaryl pentanediamine (polyamide 55), poly hexamethylene adipamide pentanediamine (polyamide 56), polypentamethylene suberamide (polyamides Amine 58), polypentamethylene azelamide (polyamide 59), poly- decanedioyl pentanediamine (polyamide 510), two acyl pentanediamine of poly- dodecane (polyamide 512), polybutadiene acyl hexamethylene diamine (polyamide 6 4), poly- glutaryl hexamethylene diamine (polyamide 6 5), polyhexamethylene adipamide (polyamide 66), poly- suberoyl hexamethylene diamine (polyamide 6 8), poly-hexamethylene azelamide (polyamide 6 9), polyhexamethylene sebacamide (polyamide 610), nylon 612 (polyamide 612), two acyl hexamethylene diamine (polyamide 6 14) of the poly- tetradecane, poly- ten Six alkane, two acyl hexamethylene diamine (polyamide 6 16), two acyl hexamethylene diamine (polyamide 6 18) of poly- octadecane, polynonamethylene adipamide (polyamide 96), poly- suberoyl nonamethylene diamine (polyamide 98), poly- nonanedioyl nonamethylene diamine (polyamide 99), poly- decanedioyl nonamethylene diamine (polyamide 910), poly- two acyl nonamethylene diamine (polyamide 912) of dodecane, polydecamethylene adipamide (polyamide 106), poly- suberoyl decamethylene diamine (polyamide 108), poly- nonanedioyl decamethylene diamine (polyamide 109), nylon 1010 (polyamide 1010), two acyl of poly- dodecane Decamethylene diamine (polyamide 1012), poly hexamethylene adipamide dodecamethylene diamine (polyamide 126), poly- suberoyl dodecamethylene diamine (polyamide 128), poly- nonanedioyl dodecamethylene diamine (polyamide 129), poly- decanedioyl dodecamethylene diamine (polyamide 1210), poly- dodecane two The homopolymers such as acyl lauryl amine (polyamide 1212) have used copolymer obtained from a variety of starting monomers for forming these polyamide Deng.
Among these, from each physical property such as mechanical property, the heat resistances for substantially ensuring gained stacking pipe, economy obtains and holds From the perspective of Yi Du, it is preferably selected from by poly- undecanoic amide (polyamide 11), poly- dodecane amide (polyamide 12), gathers oneself Two acyl hexamethylene diamines (polyamide 66), polyhexamethylene sebacamide (polyamide 610), nylon 612 (polyamide 612), Nylon 1010 (polyamide 1010), two acyl decamethylene diamine (polyamide 1012) of poly- dodecane and two acyl lauryl amine of poly- dodecane (polyamide 1212) composition group at least one kind of homopolymer, and/or used it is a variety of formed these polyamide raw material lists Copolymer obtained from body.
As the manufacturing device of fatty polyamide (A), batch reaction kettle, single-channel type~multi-groove type company can be enumerated The mixings reaction such as continuous reaction unit, tubulose continuous reaction apparatus, single-bolt type mixing extruder, double-screw type mixing extruder is squeezed Polyamide manufacturing device well known to machine etc. out.As polymerization, melt polymerization, polymerisation in solution, solid phase etc. can be used Well known method repeats normal pressure, decompression, pressurized operation are polymerize.These polymerizations can be used alone or Appropriately combined use.
In addition, from the engineering properties for ensuring gained stacking pipe and viscosity proper range when melting is made to ensure to be laminated From the perspective of the ideal forming of pipe, according to JIS K-6920 in 96% sulfuric acid, 1%, 25 DEG C of polymer concentration of condition The relative viscosity of the fatty polyamide (A) of lower measurement is preferably 1.5 or more and 5.0 or less, more preferably 2.0 or more and 4.5 Below.
About fatty polyamide (A), the terminal amino group concentration of the average 1g polyamide is denoted as [A] (μ eq/g), will be last When carboxylic end group concentration is denoted as [B] (μ eq/g), from the viewpoint of the adhesiveness between layers and its durability for substantially ensuring stacking pipe, [A] > [B]+5, more preferably [A] > [B]+10 are preferably satisfied, further preferably [A] > [B]+15 is (hereinafter, sometimes referred to as end Modified fat polyamide).In turn, from the viewpoint of generating the melt stability of polyamide, inhibition gelling material, preferably [A]>20, more preferably 30<[A]<120.
It should be noted that terminal amino group concentration [A] (μ eq/g) can be by being dissolved in phenol/methanol for the polyamide Mixed solution is simultaneously titrated with the hydrochloric acid of 0.05N to measure.End carboxy concentration [B] (μ eq/g) can be by by the polyamides Amine is dissolved in benzylalcohol and is titrated with the sodium hydroxide solution of 0.05N to measure.
Terminal-modified fatty polyamide in the presence of amine by utilizing melt polymerization, molten for foregoing polyamides raw material Method well known to liquid polymerization, solid phase etc. is polymerize or is copolymerized to manufacture.Alternatively, passing through the presence in amine after polymerisation Lower progress melting mixing manufactures.Like this, amine can polymerization when any stage or polymerization after, melting mixing when Any stage be added, but in view of stacking pipe adhesiveness between layers when, preferably polymerization when stage be added.
As above-mentioned amine, monoamine, diamines, triamine, polyamines can be enumerated.In addition, other than amine, without departing from upper In the case where the range for stating end group concentration conditions, the carboxylic acids such as monocarboxylic acid, dicarboxylic acids, tricarboxylic acids can be added as needed Class.These amines, carboxylic acids can add simultaneously, can also add respectively.In addition, the amine of following illustrations, carboxylic acids can be with Using one kind or two or more.
As the concrete example of monoamine to be added, can enumerate methylamine, ethamine, propylamine, butylamine, amylamine, hexylamine, heptyl amice, Octylame, 2 ethyl hexylamine, nonyl amine, decyl amine, undecyl amine, lauryl amine, tridecyl amine, tetradecylamine, pentadecane The aliphatic monoamines such as base amine, hexadecylamine, octadecylamine, oleyl amine, eicosyl amine, docosyl amine；Ring The ester ring types monoamine such as hexylamine, methyl cyclohexylamine；The aromatic series monoamines such as benzylamine, beta-phenyl methylamine；N, TMSDMA N dimethylamine, N, N- diethyl Amine, N, N- di-n-propylamine, N, N- dibutyl amine, N, N- dihexylamine, N, the symmetrical secondary amine such as N- dioctylamine；N- methyl-N- ethamine, N- first Base-N- butylamine, N- methyl-N-dodecyl amine, N- methyl-N- octadecylamine, N- ethyl-N- hexadecylamine, N- ethyl- N- octadecylamine, N- propyl-N- hexadecylamine, N- propyl-N- benzyl amine etc. mix secondary amine.1 kind or 2 can be used in they Kind or more.
As the concrete example of added diamines, 1,2- ethylenediamine, 1,3- propane diamine, Putriscine, 1 can be enumerated, 5- pentanediamine, 1,6- hexamethylene diamine, 1,7- heptamethylene diamine, 1,8- octamethylenediamine, 1,9-nonamethylene diamine, 1,10- decamethylene diamine, 1,11- hendecane Diamines, 1,12- dodecamethylene diamine, 1,13- tridecane diamine, 1,14- tetradecane diamines, 1,15- pentadecane diamines, 1,16- ten Six alkane diamines, 1,17- heptadecane diamines, 1,18- octadecamethylene diamine, 2- methyl-1,5- pentanediamine, 3- methyl-1,5- pentanediamine, 2- methyl-1,8- octamethylenediamine, 2,2,4- trimethyl -1,6- hexamethylene diamine, 2,4,4- trimethyl -1,6- hexamethylene diamine, 5- methyl-1,9- The aliphatic diamines such as nonamethylene diamine；Bis- (amino methyl) hexamethylenes of 1,3-, bis- (amino methyl) hexamethylenes of 1,4-, bis- (4- amino rings Hexyl) methane, bis- (4- aminocyclohexyl) propane of 2,2-, bis- (3- methyl -4- aminocyclohexyl) methane, bis- (the 3- methyl-of 2,2- 4- aminocyclohexyl) propane, 5- amino -2,2,4- trimethyl -1- cyclopentanemethylamine, 5- amino -1,3,3- trimethyl-cyclohexane Methylamine, bis- (aminopropyl) piperazines, bis- (amino-ethyl) piperazines, bis- (amino methyl) norbornanes of 2,5-, bis- (the amino first of 2,6- Base) the ester ring types diamines such as norbornane, bis- (amino methyl) tristanes of 3,8-, bis- (amino methyl) tristanes of 4,9-；Between The aromatic diamines such as benzene dimethylamine, p dimethylamine.They can be used one kind or two or more.
As the concrete example of triamine to be added, 1,2,3- triaminopropanes, 1,2,3- triamido -2- methyl can be enumerated Propane, 1,2,4- triamido butane, 1,2,3,4- tetramino butane, 1,3,5- triamido hexamethylene, 1,2,4- triamido hexamethylene Alkane, 1,2,3- triamido hexamethylene, 1,2,4,5- tetramino hexamethylene, 1,3,5- triaminobenzene, 1,2,4- triaminobenzene, 1,2, 3- triaminobenzene, 1,2,4,5- tetramino benzene, 1,2,4- triamido naphthalene, 2,5,7- triamido naphthalene, 2,4,6- triamido pyridine, 1, 2,7,8- tetramino naphthalene etc., 1,4,5,8- tetramino naphthalene.They can be used one kind or two or more.
As long as added polyamines has multiple primary amino group (- NH2) and/or secondary amino group (- NH-) compound, Such as polyalkyleneimine, polyalkylene polyamine, polyvinylamine, polyallylamine can be enumerated etc..The amino for having reactive hydrogen is The reflecting point of polyamines.
Polyalkyleneimine is by making the alkylidenes alkenyl imines such as ethylenimine, propylidene imines carry out ionic polymerization Method or make that the polymer moieties hydrolyze or method etc. of complete hydrolysis manufactures after polymerizeing alkylated oxazoline quinoline.As poly- Alkylene polyamine can enumerate such as diethylenetriamines, trien, penten or ethylenediamine and more The reactant etc. of functional compound.For example poly- (N- vinyl first is made and polymerizeing N- vinyl formamide in polyvinylamine Amide) after, polymer moieties hydrolysis or complete hydrolysis are obtained with acid such as hydrochloric acid.Polyallylamine is generally by making allylamine Demineralizing acid is removed after the hydrochloride polymerization of monomer to obtain.They can be used one kind or two or more.Among these, preferably poly- Asia Alkyl imino.
As polyalkyleneimine, can enumerate ethylenimine, propylidene imines, 1,2- butyleneimine, 2,3- The carbon numbers such as butyleneimine, 1,1- dimethylethylene imines be 2 or more and 8 alkylene imines below in a kind or 2 kinds with Homopolymer, copolymer obtained from above being polymerize as well-established law.Among these, more preferably polyethylene imine.Poly- alkylene Base imines can be using alkylene imine as raw material and make the branch obtained from its ring-opening polymerisation comprising primary amine, secondary amine and tertiary amine Chain polyalkyleneimine or using alkylated oxazoline quinoline as raw material and obtained from polymerizeing it only comprising primary amine and secondary amine Any one of straight chain type polyalkyleneimine, the structure for being cross-linked into three-dimensional shape.In turn, ethylenediamine, propane diamine, two be may include Ethylenetriamine, trien, tetren, dipropylenetriamine, tri propylidene tetramine, two (hexa-methylenes) three Amine, aminopropyl ethylenediamine, double aminopropyl ethylenediamines etc..About polyalkyleneimine, it is typically due to included nitrogen-atoms On active hydrogen atom reactivity, other than with tertiary amino, also have the primary amino group with active hydrogen atom, secondary amino group (imino group).
Nitrogen-atoms numbers in polyalkyleneimine are not particularly limited, and preferably 4 or more and 3,000 or less, more preferably 8 Above and 1,500 or less, further preferably 11 or more and 500 or less.In addition, the number-average molecular weight of polyalkyleneimine is preferred It is 100 or more and 20,000 or less, more preferably 200 or more and 10,000 or less, further preferably 500 or more and 8,000 Below.
On the other hand, as added carboxylic acids, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, pungent can be enumerated Acid, capric acid, n-nonanoic acid, hendecanoic acid, lauric acid, tridecanoic acid, myristic acid, nutmeg olefin(e) acid, palmitinic acid, stearic acid, oleic acid, The aliphatic monocarboxylic acids such as linoleic acid, arachidic acid, behenic acid, erucic acid；The ester ring types list carboxylic such as cyclohexane-carboxylic acid, methylcyclohexanecarboxylic acid Acid；The aromatic monocarboxylates such as benzoic acid, toluic acid, ethyl benzoate, phenylacetic acid；Malonic acid, succinic acid, glutaric acid, oneself Diacid, pimelic acid, suberic acid, azelaic acid, decanedioic acid, heneicosanedioic acid, dodecanedioic acid, hexadecandioic acid (hexadecane diacid), hexadecene two Acid, octadecane diacid, octadecene diacid, eicosane diacid, octadecene dicarboxylic acid, docosandioic acid, diglycolic acid, 2,2, The aliphatic dicarboxylic acids such as 4- trimethyladipic acid, 2,4,4- trimethyladipic acid；1,3- cyclohexane dicarboxylic acid, 1,4- hexamethylene two The ester ring types dicarboxylic acids such as carboxylic acid, norbornane dicarboxylic acids；Terephthalic acid (TPA), M-phthalic acid, phthalic acid, sub- dimethylbenzene Base dicarboxylic acids, to aromatic series two such as xylylene dicarboxylic acids, 1,4- naphthalenedicarboxylic acid, 2,6- naphthalenedicarboxylic acid, 2,7- naphthalenedicarboxylic acids Carboxylic acid；1,2,4- butane tricarboxylic acid, 1,3,5- pentanetricarboxylic, 1,2,6- hexane tricarboxylic acids, 1,3,6- hexane tricarboxylic acids, 1,3, The tricarboxylic acids such as 5- cyclohexanetricarboxylic acid, trimesic acid.They can be used one kind or two or more.
The dosage of added amine considers to want terminal amino group concentration, the end of the terminal-modified fatty polyamide of manufacture Carboxylic end group concentration and relative viscosity are suitably determined by well known method.In general, sufficient reactive, easy to manufacture from obtaining From the perspective of polyamide with desired viscosity, (monomer or monomer of repetitive unit are constituted relative to 1 mole of polyamide raw materials 1 mole of unit), the additive amount of amine is preferably 0.5meq/ moles or more and 20meq/ moles or less, more preferably 1meq/ rubs You it is above and 10meq/ moles or less (about the equivalent (eq) of amino, by with carboxyl with 1:1 reacts and forms amide groups Amino amount is denoted as 1 equivalent).
It is dense in order to meet end group among foregoing illustrative amine for terminal-modified fatty polyamide The condition of degree, preferably in polymerization, addition diamines and/or polyamines are more preferably selected from from the viewpoint of inhibiting gel to generate It is at least one kind of in the group be made of aliphatic diamine, ester ring type diamines and polyalkyleneimine.
In addition, terminal-modified fatty polyamide can be terminal groups in the case where meeting above-mentioned end radical concentration The mixture of the different two or more polyamide of group's concentration.At this point, the terminal amino group concentration of polyamide compound, terminal carboxyl group are dense Degree is determined according to the terminal amino group concentration for the polyamide for constituting mixture, end carboxy concentration and its compounding ratio.
In order to improve the flexibility of fatty polyamide (A), aftermentioned polyamide 6 composition (B1), polyamide are preferably added The plasticizer recorded in 6/66/12 composition (B2).
From the viewpoint of substantially ensuring the flexibility that pipe is laminated, low-temperature impact resistance, the content of plasticizer is relative to rouge 100 mass parts of fat polyamide (A) be preferably 1 mass parts or more and 30 below the mass, more than more preferably 2 mass parts and 20 Below the mass.
In addition, preferably adding modified impact material, especially to improve the low-temperature impact resistance of fatty polyamide (A) Be more preferably add it is recording in aftermentioned polyamide 6 composition (B1), polyamide 6/66/12 composition (B2), according to ISO The bending elastic modulus of 178 measurements is 500MPa olefin polymer below.If bending elastic modulus is more than the value, impact changes Good effect is sometimes insufficient.
From the viewpoint of substantially ensuring the mechanical strength that pipe is laminated, low-temperature impact resistance, the content of modified impact material Relative to 100 mass parts of fatty polyamide (A) be preferably 1 mass parts or more and 35 below the mass, more preferably 3 mass parts Above and 25 below the mass.
Fatty polyamide (A) can be the mixture of aforementioned homopolymers, the mixture of aforementioned copolymer, homopolymer together The mixture of polymers, alternatively, being also possible to the mixture with other polyamide resins or other thermoplastic resins.In mixture Fatty polyamide (A) content be preferably 60 mass % or more, more preferably 80 mass % or more.
As other polyamide resins, poly-meta-xylylene adipamide (polyamide MXD6) can be enumerated, is poly- to benzene two Formyl m-xylene diamine (polyamide MXDT), it is poly- between phenyl-diformyl m-xylene diamine (polyamide MXDI), poly- hexahydro terephthaldehyde Acyl m-xylene diamine (polyamide MXDT (H)), two formyl m-xylene diamine (polyamide MXDN) of poly- naphthalene, poly hexamethylene adipamide terephthaldehyde Amine (polyamide PXD6), poly- paraphenylene terephthalamide p dimethylamine (polyamide PXDT), it is poly- between phenyl-diformyl p dimethylamine's (polyamides Amine PXDI), poly- hexahydro paraphenylene terephthalamide p dimethylamine (polyamide PXDT (H)), two formyl p dimethylamine's (polyamide of poly- naphthalene PXDN), poly(p-phenylene terephthalamide) (PPTA), poly- mphenylen terephthalamide (PPIA), poly- paraphenylene terephthalamide's isophthalic Diamines (PMTA), poly (PMIA), poly- (adipyl 2,6- naphthalene dimethylamine) (polyamide 2,6-BAN6), Poly- (paraphenylene terephthalamide's 2,6- naphthalene dimethylamine) (polyamide 2,6-BANT), poly- (phenyl-diformyl 2,6- naphthalene dimethylamine) (polyamide 2,6-BANI), poly- (hexahydro paraphenylene terephthalamide's 2,6- naphthalene dimethylamine) (polyamide 2,6-BANT (H)), poly- (two formyl 2,6- naphthalene of naphthalene Dimethylamine) (polyamide 2,6-BANN), poly- (adipyl 1,3- hexamethylene dimethylamine) (polyamide 1,3-BAC6), poly- (suberoyl 1,3- hexamethylene dimethylamine (polyamide 1,3-BAC8), poly- (nonanedioyl 1,3- hexamethylene dimethylamine) (polyamide 1,3-BAC9), Poly- (decanedioyl 1,3- hexamethylene dimethylamine) (polyamide 1,3-BAC10), poly- (two acyl 1,3- hexamethylene dimethylamine of dodecane) are (poly- Amide 1,3-BAC12), poly- (paraphenylene terephthalamide's 1,3- hexamethylene dimethylamine) (polyamide 1,3-BACT), it is poly- (phenyl-diformyl 1, 3- hexamethylene dimethylamine) (polyamide 1,3-BACI), poly- (hexahydro paraphenylene terephthalamide's 1,3- hexamethylene dimethylamine) (polyamide 1,3- BACT (H)), poly- (two formyl 1,3- hexamethylene dimethylamine of naphthalene) (polyamide 1,3-BACN), poly- (1,4- adipyl hexamethylene diformazan Amine) (polyamide 1,4-BAC6), poly- (suberoyl 1,4- hexamethylene dimethylamine) (polyamide 1,4-BAC8), poly- (nonanedioyl 1,4- Hexamethylene dimethylamine) (polyamide 1,4-BAC9), poly- (decanedioyl 1,4- hexamethylene dimethylamine) (polyamide 1,4-BAC10), poly- (two acyl 1,4- hexamethylene dimethylamine of dodecane) (polyamide 1,4-BAC12), poly- (paraphenylene terephthalamide's 1,4- hexamethylene dimethylamine) (polyamide 1,4-BACT), poly- (phenyl-diformyl 1,4- hexamethylene dimethylamine) (polyamide 1,4-BACI), poly- (hexahydro is to benzene two Formyl chloride-1,4- hexamethylene dimethylamine) (polyamide 1,4-BACT (H)), poly- (two formyl 1,4- hexamethylene dimethylamine of naphthalene) (polyamide 1,4-BACN), poly- (adipyl 4,4 '-di-2-ethylhexylphosphine oxide cyclohexanediamine) (polyamide PACM6), poly- (suberoyl 4,4 '-di-2-ethylhexylphosphine oxide Cyclohexanediamine) (polyamide PACM8), poly- (nonanedioyl 4,4 '-di-2-ethylhexylphosphine oxide cyclohexanediamine) (polyamide PACM9), poly- (decanedioyl 4,4 '-di-2-ethylhexylphosphine oxide cyclohexanediamine) (polyamide PACM10), poly- (two 4,4 '-di-2-ethylhexylphosphine oxide of acyl cyclohexanediamine of dodecane) (polyamides Amine PACM12), poly- (two 4,4 '-di-2-ethylhexylphosphine oxide of acyl cyclohexanediamine of the tetradecane) (polyamide PACM14), it is poly- (two acyl 4 of hexadecane, 4 '-di-2-ethylhexylphosphine oxide cyclohexanediamine) (polyamide PACM16), poly- (two 4,4 '-di-2-ethylhexylphosphine oxide of acyl cyclohexanediamine of octadecane) (polyamide PACM18), poly- (paraphenylene terephthalamide 4,4 '-di-2-ethylhexylphosphine oxide cyclohexanediamine) (polyamide PACMT), poly- (phenyl-diformyl 4,4 '-is sub- Methyl bicycle hexamethylene diamine) (polyamide PACMI), poly- (hexahydro 4,4 '-di-2-ethylhexylphosphine oxide of paraphenylene terephthalamide cyclohexanediamine) (polyamide PACMT (H)), poly- (two 4,4 '-di-2-ethylhexylphosphine oxide of formyl cyclohexanediamine of naphthalene) (polyamide PACMN), poly- (adipyl 4,4 '-methylene Bis- (2- methyl cyclohexane diamines)) (polyamide MACM6), poly- (suberoyl 4,4 '-di-2-ethylhexylphosphine oxide (2- methyl cyclohexane diamines)) (polyamides Amine MACM8), poly- (nonanedioyl 4,4 '-di-2-ethylhexylphosphine oxide (2- methyl cyclohexane diamines)) (polyamide MACM9), poly- (decanedioyl 4,4 '- Di-2-ethylhexylphosphine oxide (2- methyl cyclohexane diamines)) (polyamide MACM10), poly- (two 4,4 '-di-2-ethylhexylphosphine oxide of acyl (2- methyl cyclohexane of dodecane Diamines)) (polyamide MACM12), poly- (two 4,4 '-di-2-ethylhexylphosphine oxide of acyl of the tetradecane (2- methyl cyclohexane diamines)) (polyamide MACM14), poly- (two 4,4 '-di-2-ethylhexylphosphine oxide of acyl of hexadecane (2- methyl cyclohexane diamines)) (polyamide MACM16), poly- (octadecane two Acyl 4,4 '-di-2-ethylhexylphosphine oxide (2- methyl cyclohexane diamines)) (polyamide MACM18), poly- (paraphenylene terephthalamide 4,4 '-di-2-ethylhexylphosphine oxide (2- Methyl cyclohexane diamines)) (polyamide MACMT), poly- (phenyl-diformyl 4,4 '-di-2-ethylhexylphosphine oxide (2- methyl cyclohexane diamines)) (polyamides Amine MACMI), poly- (4,4 '-di-2-ethylhexylphosphine oxide of hexahydro paraphenylene terephthalamide (2- methyl cyclohexane diamines)) (polyamide MACMT (H)), poly- (two 4,4 '-di-2-ethylhexylphosphine oxide of formyl of naphthalene (2- methyl cyclohexane diamines)) (polyamide MACMN), poly- (adipyl 4,4 '-propylidene is bicyclic Hexamethylene diamine) (polyamide PACP6), poly- (the bicyclic hexamethylene diamine of suberoyl 4,4 '-propylidene) (polyamide PACP8), it is poly- (nonanedioyl 4, The bicyclic hexamethylene diamine of 4 '-propylidene) (polyamide PACP9), poly- (the bicyclic hexamethylene diamine of decanedioyl 4,4 '-propylidene) (polyamide PACP10), poly- (the two bicyclic hexamethylene diamine of 4,4 '-propylidene of acyl of dodecane) (polyamide PACP12), poly- (two acyl 4,4 ' of the tetradecane- The bicyclic hexamethylene diamine of propylidene) (polyamide PACP14), poly- (the two bicyclic hexamethylene diamine of 4,4 '-propylidene of acyl of hexadecane) (polyamide PACP16), poly- (the two bicyclic hexamethylene diamine of 4,4 '-propylidene of acyl of octadecane) (polyamide PACP18), poly- (paraphenylene terephthalamide 4,4 '- The bicyclic hexamethylene diamine of propylidene) (polyamide PACPT), poly- (the bicyclic hexamethylene diamine of phenyl-diformyl 4,4 '-propylidene) (polyamide PACPI), poly- (the bicyclic hexamethylene diamine of hexahydro 4,4 '-propylidene of paraphenylene terephthalamide) (polyamide PACPT (H)), it is poly- (two formyl 4 of naphthalene, The bicyclic hexamethylene diamine of 4 '-propylidene) (polyamide PACPN), poly hexamethylene adipamide isophorone diamine (polyamide IPD6), poly- suberoyl be different Isophoronediamine (polyamide IPD8), poly- nonanedioyl isophorone diamine (polyamide IPD9), poly- decanedioyl isophorone diamine Two acyl isophorone diamine (polyamide IPD12) of (polyamide IPD10), poly- dodecane, poly- paraphenylene terephthalamide's isophorone diamine (polyamide IPDT), it is poly- between phenyl-diformyl isophorone diamine (polyamide IPDI), poly- hexahydro paraphenylene terephthalamide isophorone two Amine (polyamide IPDT (H)), two formyl isophorone diamine (polyamide IPDN) of poly- naphthalene, poly- paraphenylene terephthalamide's butanediamine (polyamides Amine 4T), it is poly- between phenyl-diformyl butanediamine (polyamide 4I), poly- hexahydro paraphenylene terephthalamide butanediamine (polyamide 4T (H)), poly- naphthalene two Formyl butanediamine (polyamide 4N), poly- paraphenylene terephthalamide's pentanediamine (polyamide 5T), it is poly- between phenyl-diformyl pentanediamine (polyamide 5I), poly- hexahydro paraphenylene terephthalamide pentanediamine (polyamide 5T (H)), two formyl pentanediamine (polyamide 5N) of poly- naphthalene, poly- terephthaldehyde Acyl hexamethylene diamine (polyamide 6 T), poly-6I hexamethylene isoterephalamide (polyamide 6 I), poly- hexahydro hexamethylene terephthalamide (polyamide 6T (H)), two formyl hexamethylene diamine (polyamide 6 N) of poly- naphthalene, poly- (paraphenylene terephthalamide's 2 methyl pentamethylenediamine) (polyamide M5T), it is poly- ( Phenyl-diformyl 2 methyl pentamethylenediamine) (polyamide M5I), poly- (hexahydro paraphenylene terephthalamide 2 methyl pentamethylenediamine) (polyamide M5T (H)), poly- (two formyl 2 methyl pentamethylenediamine (polyamide M5N) of naphthalene, poly- hexahydro paraphenylene terephthalamide nonamethylene diamine (polyamide 9T (H)), Poly- (hexahydro paraphenylene terephthalamide's 2- methyl octamethylenediamine) (polyamide M8T (H)), it is poly- between phenyl-diformyl trimethylhexane diamine (polyamide TMHI), poly- hexahydro paraphenylene terephthalamide trimethylhexane diamine (polyamide TMHT (H)), it is poly- between phenyl-diformyl decamethylene diamine (polyamide 10I), poly- hexahydro paraphenylene terephthalamide decamethylene diamine (polyamide 10T (H)), it is poly- between phenyl-diformyl hendecane diamines (polyamide 11I), Poly- hexahydro paraphenylene terephthalamide hendecane diamines (polyamide 11T (H)), it is poly- between phenyl-diformyl dodecamethylene diamine (polyamide 12I), poly- Hexahydro paraphenylene terephthalamide dodecamethylene diamine (polyamide 12T (H)) has used obtained from the starting monomer of these a variety of polyamide Copolymer etc..They can be used one kind or two or more.
In addition, high density polyethylene (HDPE) (HDPE), the poly- second of middle density can be enumerated as mixed other thermoplastic resins Alkene (MDPE), low density polyethylene (LDPE) (LDPE), straight-chain low density polyethylene (LDPE) (LLDPE), ultra-high molecular weight polyethylene (UHMWPE), polypropylene (PP), polybutene (PB), polymethylpentene (TPX), ethylene/propene copolymer (EPR), ethylene/butylene Copolymer (EBR), ethylene/vinyl acetate (EVA), ethylene/acrylic acid copolymer (EAA), ethylene/methacrylic acid Copolymer (EMAA), ethylene/methyl acrylate copolymer (EMA), ethylene/methacrylic acid methyl terpolymer (EMMA), ethylene/ The polyolefin-based resins such as ethyl acrylate copolymer (EEA)；Polystyrene (PS), syndiotactic polystyrene (SPS), methyl-prop E pioic acid methyl ester/styrol copolymer (MS), methyl methacrylate/styrene/butadiene copolymers (MBS), styrene/fourth two Alkene copolymer (SBR), styrene/isoprene copolymer (SIR), styrene/isoprene/butadiene copolymer (SIBR), Styrene/butadiene/styrene copolymers (SBS), styrene/isoprene/styrene copolymer (SIS), styrene/second The polystyrenes trees such as alkene/butylene/styrene copolymer (SEBS), styrene/ethylene/propylene/styrene copolymer (SEPS) Rouge；Said polyolefins system resin, polystyrene resin containing the functional groups such as carboxyl and its salt, anhydride group, epoxy group；Poly- pair Benzene dicarboxylic acid butanediol ester (PBT), polyethylene glycol isophthalate (PEI), gathers polyethylene terephthalate (PET) (ethylene glycol terephthalate/ethylene isophthalate) copolymer (PET/PEI), polypropylene terephthalate (PTT), polycyclohexylene's diformazan alcohol ester (PCT), polyethylene naphthalate (PEN), poly- naphthalenedicarboxylic acid fourth two The polyester based resins such as alcohol ester (PBN), polyarylate (PAR), liquid crystal polyester (LCP), polylactic acid (PLA), polyglycols sour (PGA)；It is poly- The polyether systems resins such as acetal (POM), polyphenylene oxide (PPO)；The polysulfones systems such as polysulfones (PSU), polyether sulfone (PESU), polyphenylsulfone (PPSU) Resin；The polythiaethers system resins such as polyphenylene sulfide (PPS), poly thioether sulfone (PTES)；Polyketone (PK), polyether-ketone (PEK), polyether-ether-ketone (PEEK), polyether ketone ketone (PEKK), polyethers ether ether ketone (PEEEK), polyether ether ketone ketone (PEEKK), polyether ketone ketone ketone (PEKKK), The polyketone system such as polyetherketoneetherketoneketone (PEKEKK) resin；Polyacrylonitrile (PAN), polymethacrylonitrile, acrylonitrile/styrene copolymerized Object (AS), methacrylonitrile/styrol copolymer, acrylonitrile/butadiene/styrene copolymer (ABS), acrylonitrile/butadiene The polynitriles system such as copolymer (NBR) resin；The poly- methyl such as polymethyl methacrylate (PMMA), polyethyl methacrylate (PEMA) Acrylic ester resin；Polyvinyl alcohol (PVA), polyvinylidene chloride (PVDC), polyvinyl chloride (PVC), vinyl chloride/inclined two chloroethene The polyvinyl systems resins such as alkene copolymer, vinylidene chloride/methyl acrylate copolymer；Cellulose acetate, cellulose butyrate etc. Cellulose-based resin；The polycarbonate-based resins such as polycarbonate (PC)；Thermoplastic polyimide (TPI), polyetherimide, polyester The polyimides system resins such as acid imide, polyamidoimide (PAI), imide；Thermoplastic urethane-based resin is gathered Amide elastomer, polyurethane elastomer, polyester elastomer etc. according to circumstances can enumerate polyvinylidene fluoride (PVDF), poly- fluorine Change vinyl acetate (PVF), polytetrafluoroethylene (PTFE) (PTFE), polychlorostyrene vinyl fluoride (PCTFE), tetrafluoroethylene/ethylene copolymer (ETFE), second Alkene/chlorotrifluoroethylene (ECTFE), tetrafluoroethylene/hexafluoropropylene copolymer (FEP), tetrafluoroethylene/hexafluoropropylene/partially Fluoride copolymers (THV), tetrafluoroethylene/hexafluoropropylene/vinylidene fluoride/perfluor (alkyl vinyl ether) copolymer, four Vinyl fluoride/perfluor (alkyl vinyl ether) copolymer (PFA), tetrafluoroethylene/hexafluoropropylene/perfluor (alkyl vinyl ether) copolymerization The fluorine resins such as object, chlorotrifluoroethylene/perfluor (alkyl vinyl ether)/TFE copolymer (CPT).They can be used 1 Kind or two or more.
In turn, as needed, antioxidant, heat stabilizer, ultraviolet radiation absorption can be added into fatty polyamide (A) Agent, Photostabilised dose, lubricant, inorganic filling material, antistatic agent, fire retardant, crystallization promoter, colorant etc..
2. (b) layer
(b) layer that pipe is laminated includes polyamide 6 composition (B1) and/or polyamide 6/66/12 composition (B2).
[polyamide 6 composition (B1), polyamide 6/66/12 composition (B2)]
Polyamide 6 composition (B1) contains polycaprolactam (polyamide 6) 50 mass % or more and 98 mass % or less, plasticising 1 mass % of agent (B3) or more and 20 mass % or less and according to ISO 178 measure bending elastic modulus be 500MPa or less 1 mass % of olefin polymer (B4) or more and 30 mass % or less (hereinafter sometimes referred to polyamide 6 composition (B1)).
Polycaprolactam (polyamide 6) is in main chain with amido bond (- CONH-) and with following formula (- CO- (CH2)6- NH-)nShown in hexanoyl amine unit polyamide (hereinafter sometimes referred to polyamide 6).
Polyamide 6/66/12 composition (B2) contains 50 mass % of polyamide compound or more and 98 mass % or less, increasing Mould agent (B3) 1 mass % or more and 20 mass % or less and according to the bending elastic modulus that ISO 178 is measured be 500MPa with Under 1 mass % of olefin polymer (B4) or more and 30 mass % hereinafter, the polyamide compound include it is poly- (caproamide/oneself Two acyl hexamethylene diamines/dodecane amide) (polyamide 6/66/12) and selected from by polyhexamethylene sebacamide (polyamide 610), poly- 12 Two acyl hexamethylene diamine (polyamide 612) of alkane, poly- decanedioyl nonamethylene diamine (polyamide 910), two acyl nonamethylene diamine (polyamide of poly- dodecane 912), nylon 1010 (polyamide 1010), two acyl decamethylene diamine (polyamide 1012) of poly- dodecane and two acyl of poly- dodecane At least one kind of polyamide in the group of lauryl amine (polyamide 1212) composition is (hereinafter, sometimes referred to as polyamide 6/66/12 composition (B2))。
Poly- (caproamide/hexamethylene adipamide/dodecane amide) (polyamide 6/66/12) is that have amido bond in main chain (- CONH-) and there is following formula (- CO- (CH2)6-NH-)nShown in hexanoyl amine unit, following formula (- NH- (CH2)6-NH-CO- (CH2)4-CO-)nShown in hexamethyleneadipamide unit and following formula (- CO- (CH2)11-NH-)nShown in dodecane amide list The polyamide copolymer (hereinafter sometimes referred to polyamide 6/66/12) of member.Polyamide 6/66/12 can be by making 6-aminocaprolc acid And/or caprolactam is total to the salt and 12 amino dodecanoic acid and/or lauric lactam of hexamethylene diamine and adipic acid It is poly- to obtain.
For polyamide 6/66/12, go out from the viewpoint of the adhesiveness between layers and its durability that substantially ensure stacking pipe Hair, relative to total 100 mass % of hexanoyl amine unit, hexamethyleneadipamide unit and dodecanoyl amine unit, caproamide list Member and the total unit of hexamethyleneadipamide unit and the mass ratio of dodecanoyl amine unit are preferably 81 mass %:19 mass % Above and 95 mass %:5 mass % or less, more preferably 83 mass %:17 mass % or more and 92 mass %:8 mass % with Under.
For polyamide 6/66/12, it is copolymerized from the heat resistance and Ethylene/vinyl acetate for substantially ensuring stacking pipe From the perspective of shape stability when object saponified (C) is coextruded, relative to hexanoyl amine unit and hexamethylene adipamide The mass ratio of total 100 mass % of unit, hexanoyl amine unit and hexamethyleneadipamide unit is preferably 80 mass %:20 matter Measure % or more and 95 mass %:5 mass % or less, more preferably 82 mass %:18 mass % or more and 93 mass %:7 matter Measure % or less.
Polyamide 6/66/12 composition (B2) contains: comprising polyamide 6/66/12 and selected from by polyhexamethylene sebacamide (polyamide 610), nylon 612 (polyamide 612), poly- decanedioyl nonamethylene diamine (polyamide 910), poly- dodecane Two acyl nonamethylene diamines (polyamide 912), nylon 1010 (polyamide 1010), two acyl decamethylene diamine (polyamide of poly- dodecane 1012) polyamide compound of at least one kind of polyamide and in the group of poly- two acyl lauryl amine (polyamide 1212) of dodecane composition (hereinafter sometimes referred to polyamide compound).
Polyhexamethylene sebacamide (polyamide 610), nylon 612 (polyamide 612), poly- decanedioyl nonyl two Amine (polyamide 910), two acyl nonamethylene diamine (polyamide 912) of poly- dodecane, nylon 1010 (polyamide 1010), poly- 12 Two acyl decamethylene diamine (polyamide 1012) of alkane and two acyl lauryl amine (polyamide 1212) of poly- dodecane be long-chain fat polyamide (with It is sometimes referred to as long-chain fat polyamide down), among these, from the adhesiveness between layers and its durability for sufficiently obtaining stacking pipe Viewpoint is set out, preferably polyhexamethylene sebacamide (polyamide 610), nylon 612 (polyamide 612).
About the mixed proportion of both polyamide 6/66/12 and long-chain fat polyamide, from obtaining mechanical property, resistance to Chemical agents and the excellent stacking pipe of flexibility, and from the perspective of sufficiently obtaining adhesiveness between layers and its durability, relatively In total 100 mass % of the polyamide compound of polyamide 6/66/12 and long-chain fat polyamide, polyamide 6/66/12 Content be preferably 50 mass % or more and 90 mass % or less, more preferably 55 mass % or more and 85 mass % or less, into One step is preferably 60 mass % or more and 80 mass % hereinafter, the content of long-chain fat polyamide is preferably 10 mass % or more And 50 below mass %, more preferably 15 mass % or more and 45 mass % or less, further preferably 20 mass % or more and 40 mass % or less.
As polyamide 6, the manufacturing device of polyamide 6/66/12 and long-chain fat polyamide, aliphatic can be enumerated The known polyamide manufacturing device recorded in the explanation of polyamide (A).As polyamide 6, polyamide 6/66/12 and long-chain fat The manufacturing method of polyamide can enumerate the known method recorded in the explanation of fatty polyamide (A).
In addition, from the engineering properties for ensuring gained stacking pipe and viscosity proper range when melting is made to ensure to be laminated From the perspective of the ideal forming of pipe, according to JIS K-6920 in 96% sulfuric acid, 1%, 25 DEG C of polymer concentration of condition The relative viscosity of the polyamide 6 of lower measurement, polyamide 6/66/12 and long-chain fat polyamide be preferably 1.5 or more and 5.0 with Under, more preferably 2.0 or more and 4.5 or less.
About polyamide 6, polyamide 6/66/12 and long-chain fat polyamide, by the end ammonia of the average 1g polyamide It is viscous from the interlayer for sufficiently really stewing stacking pipe when base concentration is denoted as [A] (μ eq/g), end carboxy concentration is denoted as to [B] (μ eq/g) From the perspective of connecing property and its durability, [A] > [B]+5, more preferably [A] > [B]+10, further preferably [A] are preferably satisfied > [B]+15 (hereinafter sometimes referred to terminal-modified polyamide).In turn, from the melt stability of polyamide, inhibition gel produce From the perspective of life, preferably [A]>20, more preferably 30<[A]<120.
Terminal-modified polyamide in the presence of amine using melt polymerization, solution by gathering foregoing polyamides raw material Method well known to conjunction, solid phase etc. is polymerize or is copolymerized to manufacture.Alternatively, after polymerisation by the presence of amine into Row melting mixing manufactures.Like this, amine can polymerization when any stage or polymerization after, melting mixing when appoint The meaning stage is added, but when the adhesiveness between layers in view of pipe is laminated, the stage preferably in polymerization is added.As upper Amine is stated, monoamine, diamines, triamine, polyamines can be enumerated.In addition, other than amine, without departing from above-mentioned end radical concentration In the case where the range of condition, the carboxylic acids such as monocarboxylic acid, dicarboxylic acids, tricarboxylic acids can be added as needed.These amines, carboxylic acid Class can add simultaneously, can also add respectively.In addition, aforementioned aliphatic polyamides can be enumerated as these amines, carboxylic acids The substance recorded in the explanation of amine (A), they can be used one kind or two or more.
As the plasticizer (B3) in polyamide 6 composition (B1), polyamide 6/66/12 composition (B2), can enumerate Benzene sulfonic acid alkylamide, toluenesulfonic acid alkylamide, alkyl parabens class etc..
As benzene sulfonic acid alkylamide, benzene sulfonic acid propionamide, benzene sulfonic acid butyramide, benzene sulfonic acid 2- ethyl hexyl can be enumerated Amide etc..As toluenesulfonic acid alkylamide, N- ethyl o-toluene sulfonic acid butyramide, N- ethyl p-methyl benzenesulfonic acid can be enumerated Butyramide, N- ethyl o-toluene sulfonic acid 2- ethyl hexyl amide, N- ethyl p-methyl benzenesulfonic acid 2- ethyl hexyl amide etc..As hydroxy benzenes Alkyl formate class, can enumerate septichen ethylhexyl, P-hydroxybenzoic acid ethylhexyl, septichen oneself Base last of the ten Heavenly stems ester, P-hydroxybenzoic acid hexyl last of the ten Heavenly stems ester, septichen ethyl last of the ten Heavenly stems ester, P-hydroxybenzoic acid ethyl last of the ten Heavenly stems ester, adjacent hydroxyl Benzoic acid octyl monooctyl ester, P-hydroxybenzoic acid octyl monooctyl ester, septichen decyl dodecyl ester, the P-hydroxybenzoic acid last of the ten Heavenly stems Base dodecyl ester, Methyl Salicylate, methyl p-hydroxybenzoate, septichen butyl ester, P-hydroxybenzoic acid The own ester of butyl ester, septichen, the own ester of P-hydroxybenzoic acid, septichen n-octyl, P-hydroxybenzoic acid n-octyl, Septichen last of the ten Heavenly stems ester, P-hydroxybenzoic acid last of the ten Heavenly stems ester, septichen dodecyl ester, P-hydroxybenzoic acid dodecyl Ester etc..They can be used one kind or two or more.
Among these, the preferably benzene sulfonic acids alkylamide, N- second such as benzene sulfonic acid butyramide, benzene sulfonic acid 2- ethyl hexyl amide The toluenesulfonic acids alkylamides, para hydroxybenzene such as base p-methyl benzenesulfonic acid butyramide, N- ethyl p-methyl benzenesulfonic acid 2- ethyl hexyl amide The alkyl parabens classes such as formic acid ethylhexyl, P-hydroxybenzoic acid hexyl last of the ten Heavenly stems ester, P-hydroxybenzoic acid ethyl last of the ten Heavenly stems ester, more Preferably benzene sulfonic acid butyramide, P-hydroxybenzoic acid ethylhexyl, P-hydroxybenzoic acid hexyl last of the ten Heavenly stems ester.
The bending bullet measured according to ISO 178 in polyamide 6 composition (B1), polyamide 6/66/12 composition (B2) Property modulus be 500MPa olefin polymer below (B4) (hereinafter sometimes referred to olefin polymer (B4)) be to improve polyamides Amine 6, polyamide 6/66/12 and long-chain fat polyamide low-temperature impact resistance and add.If olefin polymer (B4) It is more than the value according to the bending elastic modulus that ISO 178 is measured, then modified impact effect is sometimes insufficient.
As olefin polymer (B4), can enumerate (ethylene and/or propylene)/alpha-olefin based copolymer, (ethylene and/or Propylene)/(alpha, beta-unsaturated carboxylic acid and/or esters of unsaturated carboxylic acids) based copolymer, ionomer polymer, aromatic vinyl conjunction Object/conjugated diene compound based block copolymer, they can be used one kind or two or more.
Aforementioned (ethylene and/or propylene)/alpha-olefin based copolymer is the α-for being 3 or more by ethylene and/or propylene and carbon number Polymer obtained from alkene is copolymerized, the alpha-olefin for being 3 or more as carbon number, can enumerate propylene, 1- butylene, 1- penta Alkene, 1- hexene, 1- heptene, 1- octene, 1- nonene, 1- decene, 1- endecatylene, 1- dodecylene, 1- tridecylene, 1- 14 Carbene, 1- pentadecane alkene, cetene, 1- heptadecene, 1- octadecene, 19 carbene of 1-, 1- eicosylene, 3- first Base-1- butylene, 3- Methyl-1-pentene, 3- ethyl-1- amylene, 4-methyl-1-pentene, 4- methyl-1-hexene, 4,4- dimethyl- 1- hexene, 4,4- dimethyl-1- amylene, 4- ethyl-1- hexene, 3- ethyl-1- hexene, 9- methyl-1-decene, 11- methyl-1- Dodecylene, 12- ethyl-tetradecene etc..They can be used one kind or two or more.In addition it is also possible to be copolymerized Isosorbide-5-Nitrae- Pentadiene, 1,4- hexadiene, 1,5- hexadiene, 1,4- octadiene, 1,5- octadiene, 1,6- octadiene, 1,7- octadiene, 2- first Base -1,5- hexadiene, 6- methyl-1,5- heptadiene, 7- methyl-1,6- octadiene, 4- ethidine -8- methyl-1,7- nonadiene, 4,8- dimethyl -1,4,8- last of the ten Heavenly stems triolefin (DMDT), bicyclopentadiene, cyclohexadiene, cyclo-octadiene, 5- vinyl bornylene, 5- Ethidine -2- bornylene, 5- methylene -2- bornylene, 5- isopropylidene -2- bornylene, 6- chloromethyl -5- isopropenyl -2- Ice drops in bornylene, 2,3- diisopropyl fork base -5- bornylene, 2- ethidine -3- isopropylidene -5- bornylene, 2- acrylic -2,5- The polyenoid of the non-conjugated dienes such as piece alkane diene.They can be used one kind or two or more.
Aforementioned (ethylene and/or propylene)/(alpha, beta-unsaturated carboxylic acid and/or esters of unsaturated carboxylic acids) based copolymer is by ethylene And/or propylene and α, polymer obtained from beta-unsaturated carboxylic acid and/or unsaturated carboxylic acid ester monomer are copolymerized, as α, β- Unsaturated carboxylic acid monomer can enumerate acrylic acid, methacrylic acid, and as α, beta-unsaturated carboxylic acid ester monomer can enumerate this Methyl esters, ethyl ester, propyl ester, butyl ester, pentyl ester, own ester, heptyl ester, monooctyl ester, nonyl ester, the last of the ten Heavenly stems ester etc. of a little unsaturated carboxylic acids.They can make With one kind or two or more.
Aforementioned ionomer polymer is that at least part carboxyl of alkene and alpha, beta-unsaturated carboxylic acid copolymer passes through metal Obtained from the neutralization of ion is ionized.As alkene, ethylene is preferably used, as α, beta-unsaturated carboxylic acid can be excellent Choosing uses acrylic acid, methacrylic acid, but not limited thereto substance that place exemplifies, can also be copolymerized esters of unsaturated carboxylic acids list Body.In addition, metal ion can enumerate the alkali and alkaline earth metal ions such as Li, Na, K, Mg, Ca, Sr, Ba and Al, Sn, Sb, Ti, Mn, Fe, Ni, Cu, Zn, Cd etc..They can be used one kind or two or more.
In addition, aforementioned fragrance race vinyl compound/conjugated diene compound based block copolymer is comprising aromatic series second The block copolymer of alkenyl compound based polymer block and conjugated diene compound based polymer block, can be used has extremely The block of few 1 aromatic ethenyl compound based polymer block and at least one conjugated diene compound based polymer block Copolymer.In addition, the unsaturated bond in conjugated diene compound based polymer block can carry out in above-mentioned block copolymer Add hydrogen.
Aromatic ethenyl compound based polymer block shape based on the unit from aromatic ethenyl compound At polymer blocks.As aromatic ethenyl compound at this time, styrene, o-methyl styrene, first can be enumerated Base styrene, p-methylstyrene, 1,5- dimethyl styrene, 2,4- dimethyl styrene, vinyl naphthalene, vinyl anthracene, 4- Propylstyrene, 4- cyclohexylstyrenes, 4- dodecylstyrene, 2- ethyl -4- benzylstyrene, 4- (phenyl butyl) benzene Ethylene etc., they can be used one kind or two or more.In addition, aromatic ethenyl compound based polymer block can have sometimes There is the unit formed on a small quantity by other unsaturated monomers.
Conjugated diene compound based polymer block is by 1,3- butadiene, chlorobutadiene, isoprene, 2,3- diformazan Base -1,3- butadiene, 1,3- pentadiene, 4- methyl-1,3-pentylene, 1 in 1,3- hexadiene equiconjugate diene compound Kind or two or more polymer blocks formed, in the aromatic ethenyl compound/conjugated diene compound system for having carried out adding hydrogen In block copolymer, part or all of unsaturated bond part in the conjugated diene compound based polymer block is by adding hydrogen And form saturated bond.
Aromatic ethenyl compound/conjugated diene compound based block copolymer and its add the molecular structure of hydrogen object can be with It is any one of straight-chain, branched, radial or their any combination.Among these, as aromatic vinyl It closes object/conjugated diene compound based block copolymer and/or it adds hydrogen object, it is preferable to use by 1 aromatic ethenyl compound Polymer blocks and 1 conjugated diene compound based polymer block are bonded to the diblock copolymer of straight-chain, 3 polymer Block is according to aromatic ethenyl compound based polymer block-conjugated diene compound based polymer block-aromatic vinyl The sequence of based compound based polymer block is bonded to the triblock copolymer and their a kind added in hydrogen object of straight-chain Or two or more, it can enumerate and not add hydrogen or add hydrogen styrene/butadiene block copolymer, do not add hydrogen or add hydrogen styrene/isoamyl Diene block copolymer, plus hydrogen or add hydrogen styrene/butadiene/styrene block copolymers, plus hydrogen or add hydrogen styrene/ Isoprene/styrene block copolymer, plus hydrogen or add hydrogen styrene/(ethylene/butadiene)/styrene block copolymer, Not plus hydrogen or add hydrogen styrene/(isoprene/butadiene)/styrene block copolymer etc..
In addition, (ethylene and/or propylene)/alpha-olefin based copolymer, (ethylene and/or third as olefin polymer (B4) Alkene)/(alpha, beta-unsaturated carboxylic acid and/or esters of unsaturated carboxylic acids) based copolymer, ionomer polymer, aromatic vinyl conjunction It is preferable to use the polymer being modified using carboxylic acid and/or its derivative for object/conjugated diene compound based block copolymer. By being modified using this ingredient, thus in the molecule thereof comprising to polyamide 6, polyamide 6/66/12, long-chain fat race The affinity functional group of polyamide, aforementioned fatty polyamide (A).
Have as to polyamide 6, polyamide 6/66/12, long-chain fat polyamide, aforementioned fatty polyamide (A) The functional group of compatibility can enumerate carboxyl, anhydride group, carboxylate, carboxylic metallic salt, carboxylic acid imide's base, carboxylic acid amide Base, epoxy group etc..As the example of the compound comprising these functional groups, acrylic acid, methacrylic acid, Malaysia can be enumerated Acid, fumaric acid, itaconic acid, crotonic acid, mesaconic acid (Mesaconic acid), citraconic acid, glutaconate, cis- -4- cyclohexene - 1,2- dicarboxylic acids, bridge-be bicyclic-metal salt, the maleic acid list first of [2.2.1] -5- heptene -2,3- dicarboxylic acids and these carboxylic acids Ester, monomethyl itaconate, methyl acrylate, ethyl acrylate, butyl acrylate, 2-EHA, dihydroxypropyl Ethyl ester, methyl methacrylate, 2-Ethylhexyl Methacrylate, hydroxyethyl methacrylate, methacrylic acid amino second Ester, dimethyl maleate, dimethyl itaconate, maleic anhydride, itaconic anhydride, citraconic anhydride, bridge-be bicyclic-[2.2.1] -5- heptan Alkene -2,3- dicarboxylic anhydride, maleimide, n-ethylmaleimide, N- butyl maleimide, N- benzyl maleimide Amine, acrylamide, Methacrylamide, glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate Glyceride, glycidyl itoconate, citraconic acid ethylene oxidic ester etc..They can be used one kind or two or more.
The content of polyamide 6 in polyamide 6 composition (B1) is 50 mass % or more and 98 mass % hereinafter, preferably 60 mass % or more and 95 mass % are hereinafter, more preferably 70 mass % or more and 92 mass % or less.If the content of polyamide 6 Lower than aforementioned value, then the mechanical property of gained stacking pipe is sometimes poor, on the other hand, if being more than aforementioned value, gained stacking pipe Adhesiveness between layers and its durability it is sometimes poor.
The content of polyamide compound in polyamide 6/66/12 composition (B2) is 50 mass % or more and 98 mass % Hereinafter, preferably 60 mass % or more and 95 mass % are hereinafter, more preferably 70 mass % or more and 92 mass % or less.As gathered The content of amide blend is lower than aforementioned value, then the mechanical property of gained stacking pipe is sometimes poor, is more than aforementioned value on the other hand When, then the adhesiveness between layers of gained stacking pipe and its durability are sometimes poor.
The content of plasticizer (B3) in polyamide 6 composition (B1), polyamide 6/66/12 composition (B2) is 1 matter Measure % or more and 20 mass % hereinafter, preferably 2 mass % or more and 15 mass % hereinafter, more preferably 3 mass % or more and 10 mass % or less.If the content of plasticizer (B3) is lower than aforementioned value, the flexibility of gained stacking pipe is sometimes poor, another party Face, when being more than aforementioned value, the low-temperature impact resistance that pipe is laminated in gained is sometimes poor.
The content of olefin polymer (B4) in polyamide 6 composition (B1), polyamide 6/66/12 composition (B2) is 1 Quality % or more and 30 mass % hereinafter, preferably 3 mass % or more and 25 mass % hereinafter, more preferably 5 mass % or more And 20 below mass %.If the content of olefin polymer (B4) is lower than aforementioned value, low-temperature impact resistance, the layer of gained stacking pipe Between cementability and its durability it is sometimes poor, on the other hand, be more than aforementioned value when, gained be laminated pipe mechanical property sometimes compared with Difference.
Polyamide 6 composition (B1), polyamide 6/66/12 composition (B2) manufacturing method are not particularly limited, can be with Compounding various additives as needed, and use known various methods.For example, can be made by following method etc. Make: by polyamide 6 or polyamide 6/66/12 and long-chain fat polyamide and olefin polymer (B4) be added as needed Other ingredients equably carry out dry type blending with rotary drum, mixer together so that pellet reaches aforementioned mixed proportion each other, and On the other hand supply injects plasticizer (B3) using constant displacement pump from the midway of the machine barrel of the melting mixing machine to melting mixing machine, And carry out melting mixing.Single screw extrusion machine, double screw extruder, kneader, Banbury mixer can be used in melting mixing Kneading machines are waited to carry out.
Polyamide 6 composition (B1), polyamide 6/66/12 composition (B2) can containing other polyamide resins or its Its thermoplastic resin.As other polyamide resins or other thermoplastic resins, can enumerate and aforementioned fatty polyamide (A) the case where identical resin.Polyamide 6 composition (B1), polyamide 6/66/12 composition (B2) content in mixture Preferably 60 mass % or more, more preferably 70 mass % or more.
It in turn, as needed, can also the addition into polyamide 6 composition (B1), polyamide 6/66/12 composition (B2) Antioxidant, heat stabilizer, ultraviolet absorbing agent, Photostabilised dose, it is lubricant, inanimate matter packing material, antistatic agent, fire-retardant Agent, crystallization promoter, colorant, lubricant etc..
(3. c) layer
(c) layer that pipe is laminated includes that ethylene/vinyl acetate is saponified (C).
[ethylene/vinyl acetate is saponified (C)]
Ethylene/vinyl acetate saponified (C) is by using base catalyst etc. using well known method to by second The copolymer that alkene and vinyl acetate are formed, which is saponified, obtains (hereinafter sometimes referred to EVOH (C)).
In turn, from substantially ensuring that the viewpoint of melt forming, flexibility, impact resistance and anti-chemical solution permeability goes out Hair, the ethylene contents of EVOH (C) are preferably 15 moles of % or more and 60 mole of % or less, more preferably 20 moles of % or more and 55 Mole % or less, further preferably 25 moles of % or more and 45 mole of % or less.Herein, EVOH (C) is by ethylene contents difference Two or more EVOH mixture formation when, using by respective ethylene contents and mixing mass ratio calculating value contain as ethylene Amount.
In addition, from the viewpoint of obtaining good anti-chemical solution permeability, the saponification of the vinyl acetate ingredient of EVOH (C) Degree is preferably 90 moles of % or more, more preferably 95 moles of % or more, further preferably 98% mole or more, is particularly preferably 99 moles of % or more.It herein, will be by respective when EVOH (C) is formed by the mixture of the different two or more EVOH of saponification degree The value that saponification degree and mixing mass ratio calculate is as saponification degree.It should be noted that the ethylene contents and saponification degree of EVOH can lead to Nuclear magnetic resonance (NMR) method is crossed to find out.
From making viscosity when melting be in proper range so that it is guaranteed that ideal formability, will not make to melt paratonia and drop It is low, prevent forming when occur drawdown (draw down) the problems such as from the perspective of, the melt flow rate (MFR) (MFR) of EVOH (C) (210 DEG C, 2,160g load under) are preferably 0.1g/10 minutes or more and 100g/10 minutes or less, more preferably 0.3g/10 points It is more than clock and 50g/10 minutes or less, further preferably 0.5g/10 minutes or more and 20g/10 minutes or less.
As long as in addition, can also be carried out with other monomers in the range of not damaging each excellent characteristics of gained stacking pipe Copolymerization.As other monomers, vinyl formate, vinyl propionate, vinyl valerate, vinyl butyrate, isobutyric acid can be enumerated Vinyl acetate, pivalic acid vinyl acetate, vinyl caproate, sad vinyl acetate, caprate, vinyl laurate, Ethyl Myristate Enester, vinyl palmitate, stearic acid vinyl ester, isopropyl acetate alkenyl, acetic acid 1- butene esters, pivalic acid vinyl acetate, 2- ethyl The vinyl esters such as vinyl caproate, naphthenic acid vinyl acetate, vinyl benzoate, vinyl cinnamate；Propylene, 1- butylene, The alpha-olefines such as isobutene, 4-methyl-1-pentene, 1- hexene, 1- octene, 1- dodecylene；Acrylic acid, methacrylic acid, bar The unsaturation acids such as beans acid, phthalic acid, maleic acid (acid anhydride), itaconic acid (acid anhydride) or its salt or carbon number be 1 or more and 18 with Under monoalkyl esters or dialkyl esters；Acrylamide, carbon number are 1 or more and 18 N- alkyl acrylamides below, N, N- Dimethylacrylamide, 2- acrylamide propane sulfonic acid or its salt, acrylamide propyl dimethylamine or its hydrochlorate or its quaternary ammonium salt etc. Acrylic amide；Methacrylamide, carbon number are 1 or more and 18 N- alkyl methacrylamides below, N, N- dimethyl methyl Base acrylamide, 2- Methacrylamide propane sulfonic acid or its salt, Methacrylamide diemethylamine or its hydrochlorate or its quaternary ammonium The methacryls amine such as salt；The N- vinyl acyl such as n-vinyl pyrrolidone, N- vinyl formamide, N- vinyl acetamide Amine；The vinyl cyanides base class such as acrylonitrile, methacrylonitrile；Carbon number is 1 or more and 18 alkyl vinyl ethers below, hydroxyl alkane The vinyl ethers such as base vinyl ethers, alkoxyalkyl vinyl ethers；Vinyl chloride, vinylidene chloride, vinyl fluoride, inclined difluoro second The vinyl halides class such as alkene, vinyl bromide；Vinyltrimethoxysilane, vinyl methyl dimethoxysilane, vinyl-dimethyl base Methoxy silane, vinyltriethoxysilane, vinyl methyl diethoxy silane, vinyl dimethylethoxysilane, The vinyl silanes classes such as γ-methacryloxypropyl methoxy silane；Allyl acetate, allyl chloride, allyl alcohol, diformazan Base allyl alcohol, trimethyl-(3- acrylamide -3- dimethyl propyl) ammonium chloride, acrylamide-2-methyl propane sulfonic, carbonic acid second Alkenyl ethyl etc..They can be used one kind or two or more.
In addition, various additives can also be contained in EVOH (C) as needed.As the example of this additive, can arrange Enumerate antioxidant, plasticizer, heat stabilizer, ultraviolet absorbing agent, antistatic agent, lubricant, colorant, filler or other Thermoplastic resin can contain these additives in the range of not damaging each excellent characteristics of gained stacking pipe.Specifically, Can enumerate 2,5 di tert butyl hydroquinone, DBPC 2,6 ditertiary butyl p cresol, 4,4 '-thiobis (6- tert-butyl-m-cresol), 4,4 '-thiobis (6- tert-butyl phenol), 4,4 '-thiobis (3 methy 6 tert butyl phenol), 2,2 '-di-2-ethylhexylphosphine oxides (4- first Base -6- tert-butyl phenol), 2,2 '-methylene-bis(4-ethyl-6-t-butyl phenol)s, n-octadecane base-β-(3 ', 5 '-two uncles Butyl -4 '-hydroxy phenyl) propionic ester, N, N '-hexamethylene bis (3,5- di-t-butyl -4- hydroxyhydrocinnamamide), 1,1, 3- tri- (2- methyl -4- hydroxyl -5- tert-butyl-phenyl) butane, (3,5- di-t-butyl -4- hydroxyl of 1,3,5- trimethyl -2,4,6- three Base benzyl) benzene, four [methylene -3- (3 ', 5 '-di-t-butyls -4 '-hydroxy phenyl) propionic esters], four [3- of phenyl erythrityl (3,5- di-tert-butyl-hydroxy phenyl) propionic ester], three (2,4- di-tert-butyl-phenyls), two (2,4- di-tert-butyl-phenyl) seasons The antioxidants such as penta tetrol diphosphites；Ethylidene -2- cyano -3,3 '-diphenylacrylate ester, 2- (2 '-hydroxyls -5 '-first Base phenyl) benzotriazole, 2- (2 '-hydroxyls -3 '-tert-butyl -5 '-aminomethyl phenyl) -5- chlorobenzotriazole, 2- hydroxyl -4- methoxy The ultraviolet radiation absorptions such as base benzophenone, 2,2 '-dihydroxy -4- methoxy benzophenones, 2- hydroxyl -4- octyloxybenzophenone Agent；The plasticizer such as repefral, diethyl phthalate, dioctyl phthalate, phosphate；Pentaerythrite The aliphatic such as monostearate, span 40, sulphation polyolefins, ethylene glycol, glycerol, hexylene glycol are more The antistatic agents such as first alcohols；The unsaturated fatty acids such as the unsaturated fatty acid amides such as stearic amide, oleamide amide, ethylidene The fatty acid metal salts such as the bis-fatty acid amides such as double stearic amides, calcium stearate, magnesium stearate, zinc stearate, aluminum stearate, The lubricants such as wax, atoleine, low-molecular-weight polyolefin；The organic acids such as acetic acid, propionic acid, stearic acid, boronic acid compounds, phosphorylation Close the stabilizers such as inorganic acids based compound, the hydrotalcite metal salts such as object；Reduced iron powder class, potassium sulfite, ascorbic acid, to benzene The oxygen absorbents such as diphenol, gallic acid；The colorants such as carbon black, phthalocyanine, quinoline azone, indoline, azo pigment, colcother；Glass fibers Dimension, asbestos, wollastonite (バ ラ ス ト Na イ ト), mica, sericite, talcum, silica, kaolin, calcium silicates, montmorillonite etc. Filler etc..
In turn, EVOH (C) preferably comprises boron compound.By containing organic boron compound, it is improved from melt stability, obtains It is effective for must having from the perspective of the stacking pipe of uniform wall thickness.As boron compound, can enumerate boric acid class, borate, Borate, boron hydride class etc..As boric acid class, ortho-boric acid, metaboric acid, tetraboric acid etc. can be enumerated, as borate, can be enumerated Triethyl borate, trimethylborate etc. out can enumerate alkali metal salt, the alkaline earth gold of above-mentioned various boric acid class as borate Belong to salt, borax etc..They can be used one kind or two or more.Among these, preferably ortho-boric acid.
From the viewpoint of substantially ensure its containing it is effective, obtain the good pipe of appearance, boron compound in EVOH (C) Content is preferably 0.002 mass parts or more and 0.5 below the mass, more with boron element conversion relative to 100 mass parts of EVOH (C) More than preferably 0.005 mass parts and 0.2 below the mass.
EVOH (C) can contain phosphate cpd.It is long-term when can take into account melt-shaping by containing phosphate cpd Maneuverability, coloring resistance and adhesiveness between layers.It as phosphate cpd, is not particularly limited, phosphoric acid, phosphorous acid etc. can be used Various acid, its salt etc..As phosphate, dihydric phosphate, dibasic alkaliine, phosphate can be enumerated.They can be used a kind Or two or more.Phosphatic cation kind is also not particularly limited, preferably alkali metal salt, among these, preferably di(2-ethylhexyl)phosphate Hydrogen sodium, potassium dihydrogen phosphate, disodium hydrogen phosphate, dipotassium hydrogen phosphate.
From the viewpoint of substantially ensure its containing it is effective, obtain the good pipe of appearance, phosphate cpd in EVOH (C) Content relative to 100 mass parts of EVOH (C) with phosphate radical conversion preferably 0.02 below the mass, more preferably 0.0005 matter Measure part or more and 0.01 below the mass, more than further preferably 0.001 mass parts and 0.007 below the mass.
In addition, making in EVOH (C) containing alkali metal salt and/or alkali salt from melt stability, longtime running It is also preferred that viewpoint, which is set out,.The anion kind of salt as alkali or alkaline earth metal, does not limit, and can enumerate carboxylic acid Salt, hydroxide, carbonate, bicarbonate etc..The cation of alkali metal salt kind is not limited, can enumerate lithium salts, sodium salt, Sylvite etc. does not limit the cation kind of alkali salt, can enumerate magnesium salts, calcium salt, barium salt, beryllium salt, strontium salt etc..Specifically For, sodium acetate, lithium acetate, potassium acetate, calcium palmitate, magnesium palmitate, calcium myristate, magnesium myristate, hard can be enumerated Resin acid calcium, magnesium stearate, calcium oleate, magnesium oleate, calcium linoleate, magnesium linoleate, linolenic acid calcium, linolenic acid magnesium, sodium phosphate, phosphoric acid Lithium etc..They can be used one kind or two or more.
From the viewpoint of substantially ensure its containing it is effective, obtain the good pipe of appearance, relative to 100 mass of EVOH (C) Part, the content of alkali metal salt and/or alkali salt in EVOH (C) with metallic element conversion be preferably 0.0005 mass parts with It is upper and 0.2 below the mass, more than more preferably 0.001 mass parts and 0.1 below the mass, further preferably 0.002 matter Measure part or more and 0.05 below the mass.
In turn, in EVOH (C), in order to improve melt stability etc., in each excellent characteristics for not damaging gained stacking pipe In the range of, preferably addition is 0.01 mass parts or more and 1 hydrotalcite below the mass relative to 100 mass parts of EVOH (C) It is one kind or two or more in the antioxidants such as class compound, hindered phenolic.
(4. d) layer
(d) layer that pipe is laminated includes semiaromatic polyamide composition composition (D1) or semiaromatic polyamide composition composition (D2).
[semiaromatic polyamide composition composition (D1), semiaromatic polyamide composition composition (D2)]
Semiaromatic polyamide composition composition (D1) includes semiaromatic polyamide composition (d1) (hereinafter sometimes referred to semiaromatic adoption Amide compositions (D1)), semiaromatic polyamide composition (d1) contains diamine unit and dicarboxylic acid units, and the diamine unit includes phase The aliphatic diamine unit below of carbon number 9 or more and 13 for being 50 moles of % or more for whole diamine units, the dicarboxylic acids Unit includes the terephthalic acid units and/or naphthalenedicarboxylic acid unit for being 50 moles of % or more relative to whole dicarboxylic acid units (hereinafter sometimes referred to semiaromatic polyamide composition (d1)).
From heat resistance, chemical reagent resistance, impact resistance, the anti-chemical solution permeability etc. for substantially ensuring gained stacking pipe From the perspective of each physical property, the carbon number in semiaromatic polyamide composition (d1) is 9 or more and 13 aliphatic diamine units below Content is 50 moles of % or more, preferably 55 moles of % or more, more preferably 60 moles of % or more relative to whole diamine units.
It is 9 or more and 13 aliphatic diamine units below as carbon number, can enumerates by 1,9- nonamethylene diamine, 1, the 10- last of the ten Heavenly stems Unit derived from diamines, 1,11- hendecane diamines, 1,12- dodecamethylene diamine, 1,13- tridecane diamine etc..As long as carbon number meets Above range, then can also be containing by 2,2,4- trimethyl -1,6- hexamethylene diamines, 2,4,4- trimethyl -1,6- hexamethylene diamines, 2,4- bis- Ethyl -1,6- hexamethylene diamine, 2,2- dimethyl-g diamines, 2,3- dimethyl-g diamines, 2,4- dimethyl-g diamines, 2,5- dimethyl Heptamethylene diamine, 2- methyl-1,8- octamethylenediamine, 3- methyl-1,8- octamethylenediamine, 4- methyl-1,8- octamethylenediamine, 1,3- dimethyl -1,8- Octamethylenediamine, 1,4- dimethyl -1,8- octamethylenediamine, 2,2- dimethyl -1,8- octamethylenediamine, 2,4- dimethyl -1,8- octamethylenediamine, 3,3- Dimethyl -1,8- octamethylenediamine, 3,4- dimethyl -1,8- octamethylenediamine, 4,4- dimethyl -1,8- octamethylenediamine, 4,5- dimethyl -1,8- Octamethylenediamine, 5- methyl-1, the branched aliphatic two such as 9- nonamethylene diamine, 2- butyl -1,8- octamethylenediamine, 3- butyl -1,8- octamethylenediamine Unit derived from amine.They can be used one kind or two or more.
Above-mentioned carbon number is among 9 or more and 13 aliphatic diamine units below, from coextrusion formability and anti-chemical solution From the perspective of the balance of liquid permeability, preferably by 1,9- nonamethylene diamine, 2- methyl-1,8- octamethylenediamine, 1,10- decamethylene diamine are derivative Unit, from the viewpoint of substantially ensuring low-temperature impact resistance, the preferably unit derived from 1,12- dodecamethylene diamine.Into And by 1,9- nonamethylene diamine and 2- methyl-1, when 8- octamethylenediamine is applied in combination, go out from the viewpoint of formability and the balance of impact resistance Hair, 1,9- nonamethylene diamine unit and 2- methyl-1, the molar ratio of 8- octamethylenediamine unit be preferably 30 moles of %:70 moles of % or more and 98 moles of %:2 moles of % or less, more preferably 40 moles %:60 moles % or more and 95 mole of %:5 moles of % or less.
As long as diamines in the range of not damaging each excellent characteristics of gained stacking pipe, in semiaromatic polyamide composition (d1) Unit also may include other diamine units other than carbon number is 9 or more and 13 aliphatic diamine units below.As Other diamine units, can enumerate by 1,2- ethylenediamine, 1,3- propane diamine, Putriscine, 1,5- pentanediamine, 1,6- oneself two Amine, 1,7- heptamethylene diamine, 1,8- octamethylenediamine, 2- methyl-1,5- pentanediamine, 3- methyl-1, the aliphatic diamines such as 5- pentanediamine are derivative Unit；By 1,3- cyclohexanediamine, 1,4- cyclohexanediamine, bis- (amino methyl) hexamethylenes of 1,3-, bis- (amino methyl) rings of 1,4- Hexane, bis- (4- aminocyclohexyl) methane, bis- (4- aminocyclohexyl) propane of 2,2-, bis- (3- methyl -4- aminocyclohexyl) first Bis- (3- methyl -4- aminocyclohexyl) propane of alkane, 2,2-, 5- amino -2,2,4- trimethyl -1- cyclopentanemethylamine, amino -1 5-, 3,3- trimethyl-cyclohexane methylamine, bis- (aminopropyl) piperazines, bis- (amino-ethyl) piperazines, bis- (amino methyl) norborneols of 2,5- Bis- (amino methyl) norbornanes of alkane, 2,6-, bis- (amino methyl) tristanes of 3,8-, bis- (amino methyl) tristanes of 4,9- Unit derived from equal ester ring types diamines；By m-phenylene diamine (MPD), p-phenylenediamine, m-xylene diamine, p dimethylamine, the bis- (amino of 1,4- Methyl) naphthalene, bis- (amino methyl) naphthalenes of 1,5-, bis- (amino methyl) naphthalenes of 2,6-, bis- (amino methyl) naphthalenes of 2,7-, 4,4 '-diamino The virtues such as bis- (4- aminophenyl) propane of diphenyl methane, 2,2-, 4,4 '-diamino diphenyl sulfones, 4,4 '-diamino-diphenyl ethers Unit derived from fragrant race's diamines, they can be used one kind or two or more.The content of these other diamine units is relative to whole Diamine unit is 50 moles of % hereinafter, preferably 45 moles of % are hereinafter, more preferably 40 moles of % or less.
In addition, from each objects such as heat resistance, chemical reagent resistance, the anti-chemical solution permeabilities for substantially ensuring gained stacking pipe From the perspective of property, the content of terephthalic acid units and/or naphthalenedicarboxylic acid unit in semiaromatic polyamide composition (d1) is opposite In whole dicarboxylic acid units be 50 moles of % or more, preferably 55 moles of % or more, more preferably 60 moles of % or more.
As naphthalenedicarboxylic acid unit, can enumerate from 2,6-naphthalenedicarboxylic acid, 2,7- naphthalenedicarboxylic acid, Isosorbide-5-Nitrae-naphthalenedicarboxylic acid, 1, Unit derived from 5- naphthalenedicarboxylic acid etc..They can be used one kind or two or more.Among above-mentioned naphthalenedicarboxylic acid unit, it is contemplated that warp Ji property obtains easness, preferably by 2,6-naphthalenedicarboxylic acid, 2, unit derived from 7- naphthalenedicarboxylic acid.
As long as dicarboxyl in the range of not damaging each excellent characteristics of gained stacking pipe, in semiaromatic polyamide composition (d1) Acid unit can also include other dicarboxylic acid units other than terephthalic acid units and/or naphthalenedicarboxylic acid unit.As Other dicarboxylic acid units, can enumerate by malonic acid, dimethyl malonic acid, succinic acid, glutaric acid, adipic acid, 2- methyl oneself two Acid, pimelic acid, 2,2- dimethylated pentanedioic acid, 2,2- diethyl succinic acid, suberic acid, azelaic acid, 2,2,4 trimethyl adipic acid, 2,4,4- trimethyladipic acid, decanedioic acid, heneicosanedioic acid, dodecanedioic acid, tridecandioic acid, tetracosandioic acid, pentadecane Unit derived from the aliphatic dicarboxylic acids such as diacid, hexadecandioic acid (hexadecane diacid), octadecane diacid, eicosane diacid；By 1,3- pentamethylene two Unit derived from the ester ring types dicarboxylic acids such as carboxylic acid, 1,3- cyclohexane dicarboxylic acid, 1,4- cyclohexane dicarboxylic acid；By phthalic acid, M-phthalic acid, 1,3- phenylenedioxydiacetic acid, 1,4- phenylenedioxydiacetic acid, 4,4 '-oxygroup dibenzoic acids, two Phenylmethane -4,4 '-dicarboxylic acids, diphenylethane -4,4 '-dicarboxylic acids, diphenyl propane -4,4 '-dicarboxylic acids, diphenyl ether - The aromatic series two such as 4,4 '-dicarboxylic acids, diphenyl sulfone -4,4 '-dicarboxylic acids, 4,4 '-diphenyl dicarboxylic acids, 4,4 '-triphenyl dicarboxylic acids Unit derived from carboxylic acid, they can be used one kind or two or more.It is preferably single as derived from aromatic dicarboxylic acid among these Member.The content of these other dicarboxylic acid units is 50 moles of % hereinafter, preferably 45 moles of % relative to whole dicarboxylic acid units Hereinafter, more preferably 40 moles of % or less.In turn, can also be used in the range of being able to carry out melt-shaping trimellitic acid, The polybasic carboxylic acids such as trimesic acid, pyromellitic acid.
As long as semiaromatic polyamide composition (d1) can also wrap in the range of not damaging each excellent characteristics of gained stacking pipe Containing other units other than dicarboxylic acid units and diamine unit.As other units, can enumerate by caprolactam, in heptan The unit of the lactam derivatives such as amide, 11 lactams, lauric lactam, alpha-pyrrolidone, α-piperidones；By 6- amino oneself The aliphatic amines carboxylic acid such as acid, 7- aminoheptylic acid, 9 aminononanoic acid, 11- amino undecanoic acid, 12 amino dodecanoic acid, to ammonia Unit derived from the amino carboxylic acid of the aromatic amines yl carboxylic acid such as ylmethyl benzoic acid.They can be used one kind or two or more.Its The content of its unit on the basis of whole dicarboxylic acid units, preferably 45 moles of % or less, more preferably 40 moles of % or less, into One step is preferably 35 moles of % or less.
In turn, the manufacturing device as semiaromatic polyamide composition (d1) can enumerate batch reaction kettle, single-channel type~more Continuous reaction apparatus, tubulose continuous reaction apparatus, single-bolt type mixing extruder, double-screw type mixing extruder of slot type etc. are mixed Refine polyamide manufacturing device well known to extruder etc..As polymerization, melt polymerization can be used, polymerisation in solution, consolidate Method well known to phase-polymerization etc. repeats normal pressure, decompression, pressurized operation are polymerize.These polymerizations can be independent Using or appropriately combined use.
When manufacturing semiaromatic polyamide composition (d1), as catalyst, can add phosphoric acid, phosphorous acid, hypophosphorous acid, they Salt or ester etc..As phosphoric acid, phosphorous acid, hypophosphorous acid salt or ester, can enumerate such as phosphoric acid, phosphorous acid or hypophosphorous acid and potassium, The metal salt of sodium, magnesium, vanadium, calcium, zinc, cobalt, manganese, tin, tungsten, germanium, titanium, antimony etc.；The ammonium salt of phosphoric acid, phosphorous acid or hypophosphorous acid；Phosphoric acid, The ethyl ester of phosphorous acid or hypophosphorous acid, isopropyl ester, butyl ester, own ester, isodecyl ester, last of the ten Heavenly stems ester, stearyl ester, phenyl ester etc..They can be used 1 Kind or two or more.
Semiaromatic polyamide composition composition (D2) includes semiaromatic polyamide composition (d2) (hereinafter sometimes referred to semiaromatic adoption Amide compositions (D2)), semiaromatic polyamide composition (d2) contains diamine unit and dicarboxylic acid units, and the diamine unit includes phase The benzene dimethylamine unit and/or bis- (amino methyl) naphthalene units for being 50 moles of % or more for whole diamine units, the dicarboxyl Acid unit includes the aliphatic dicarboxylic acid below of carbon number 8 or more and 13 for being 50 moles of % or more relative to whole dicarboxylic acid units Unit (hereinafter sometimes referred to semiaromatic polyamide composition (d2)).
From heat resistance, chemical reagent resistance, impact resistance, the anti-chemical solution permeability etc. for substantially ensuring gained stacking pipe From the perspective of each physical property, benzene dimethylamine unit and/or bis- (amino methyl) naphthalene units in semiaromatic polyamide composition (d2) Content is 50 moles of % or more, preferably 60 moles of % or more, more preferably 70 moles of % or more relative to whole diamine units.
As benzene dimethylamine unit, can enumerate single as derived from O-phthalic amine, m-xylene diamine, p dimethylamine Member.They can be used one kind or two or more.Among aforementioned benzene dimethylamine unit, preferably by m-xylene diamine, terephthaldehyde Unit derived from amine.
As bis- (amino methyl) naphthalene units, can enumerate by bis- (amino methyl) naphthalenes of Isosorbide-5-Nitrae-, 1,5- bis- (amino methyls) Unit derived from bis- (amino methyl) naphthalenes of naphthalene, 2,6-, bis- (amino methyl) naphthalenes of 2,7- etc..They can be used a kind or 2 kinds with On.Among aforementioned bis- (amino methyl) naphthalene units, preferably spread out by bis- (amino methyl) naphthalenes of 1,5-, bis- (amino methyl) naphthalenes of 2,6- Raw unit.
As long as diamines in the range of not damaging each excellent characteristics of gained stacking pipe, in semiaromatic polyamide composition (d2) Unit also may include other diamine units other than benzene dimethylamine unit and/or bis- (amino methyl) naphthalene units.As Other diamine units, can enumerate by 1,2- ethylenediamine, 1,3- propane diamine, Putriscine, 1,5- pentanediamine, 1,6- oneself two Amine, 1,7- heptamethylene diamine, 1,8- octamethylenediamine, 1,9-nonamethylene diamine, 1,10- decamethylene diamine, 1,11- hendecane diamines, 1,12- dodecane two Amine, 1,13- tridecane diamine, 1,14- tetradecane diamines, 1,15- pentadecane diamines, 1,16- hexadecane diamines, 1,17- 17 Alkane diamines, 1,18- octadecamethylene diamine, 1,19- nonadecane diamines, 1,20- eicosane diamines, 2- methyl-1,5- pentanediamine, 3- first Base -1,5- pentanediamine, 2- methyl-1,8- octamethylenediamine, 2,2,4- trimethyl -1,6- hexamethylene diamine, 2,4,4- trimethyl -1,6- oneself two Amine, 5- methyl-1, unit derived from the aliphatic diamines such as 9- nonamethylene diamine；It is bis- by 1,3- cyclohexanediamine, 1,4- cyclohexanediamine, 1,3- Bis- (amino methyl) hexamethylenes of (amino methyl) hexamethylene, 1,4-, bis- (4- aminocyclohexyl) methane, bis- (the 4- amino rings of 2,2- Hexyl) propane, bis- (3- methyl -4- aminocyclohexyl) methane, 2,2- bis- (3- methyl -4- aminocyclohexyl) propane, 5- amino - It is 2,2,4- trimethyl -1- cyclopentanemethylamine, 5- amino -1,3,3- trimethyl-cyclohexane methylamine, bis- (aminopropyl) piperazines, double Bis- (amino methyl) norbornanes of (amino-ethyl) piperazine, 2,5-, bis- (amino methyl) norbornanes of 2,6-, the bis- (amino of 3,8- Methyl) unit derived from the ester ring types diamines such as tristane, bis- (amino methyl) tristanes of 4,9-；By m-phenylene diamine (MPD), to benzene Bis- (4- aminophenyl) propane of diamines, 4,4 '-diaminodiphenyl-methanes, 2,2-, 4,4 '-diamino diphenyl sulfones, 4,4 '-two Unit derived from the aromatic diamines such as aminodiphenyl base ether, they can be used one kind or two or more.Among these, preferably by Unit derived from aromatic diamine.The content of these other diamine units relative to whole diamine units be 50 moles of % hereinafter, Preferably 40 moles of % are hereinafter, more preferably 30 moles of % or less.
In addition, from each objects such as heat resistance, chemical reagent resistance, the anti-chemical solution permeabilities for substantially ensuring gained stacking pipe From the perspective of property, the content of the aliphatic dicarboxylic acid unit below of carbon number 8 or more and 13 in semiaromatic polyamide composition (d2) It is 50 moles of % or more, preferably 60 moles of % or more, more preferably 70 moles of % or more relative to whole dicarboxylic acid units.
It is 8 or more and 13 aliphatic dicarboxylic acid units below as carbon number, can enumerates by suberic acid, azelaic acid, the last of the ten Heavenly stems Unit derived from diacid, heneicosanedioic acid, dodecanedioic acid, tridecandioic acid etc..It, can also be with as long as carbon number is met the above range Containing by the branch such as 2,2- diethyl succinic acid, 2,2,4 trimethyl adipic acid, 2,4,4- trimethyladipic acid, 2- butyl octanoic acid Unit derived from chain fatty race dicarboxylic acids.They can be used one kind or two or more.
Aforementioned carbon number is among 8 or more and 13 aliphatic dicarboxylic acid units below, from coextrusion formability and anti-chemistry From the perspective of the balance of solution permeability, preferably union diacid, unit derived from decanedioic acid, from substantially ensuring the resistance to punching of low temperature From the perspective of hitting property, the preferably unit as derived from dodecanedioic acid.
As long as dicarboxyl in the range of not damaging each excellent characteristics of gained stacking pipe, in semiaromatic polyamide composition (d2) Acid unit may include other dicarboxylic acid units other than carbon number is 8 or more and 13 aliphatic dicarboxylic acid units below. As other dicarboxylic acid units, can enumerate by malonic acid, dimethyl malonic acid, succinic acid, glutaric acid, adipic acid, 2- methyl Adipic acid, pimelic acid, 2,2- dimethylated pentanedioic acid, tetracosandioic acid, pentacosandioic acid, hexadecandioic acid (hexadecane diacid), octadecane diacid, two Unit derived from the aliphatic dicarboxylic acids such as eicosane diacid；By 1,3- cyclopentane dicarboxylic acid, 1,3- cyclohexane dicarboxylic acid, 1,4- hexamethylene Unit derived from the ester ring types dicarboxylic acids such as alkane dicarboxylic acids；By terephthalic acid (TPA), M-phthalic acid, 1,4- naphthalenedicarboxylic acid, 1,5- naphthalene Dioctyl phthalate, 2,6- naphthalenedicarboxylic acid, 2,7- naphthalenedicarboxylic acid, 1,3- phenylenedioxydiacetic acid, two oxygroup diethyl of 1,4- phenylene Acid, 4,4 '-oxygroup dibenzoic acids, diphenyl methane -4,4 '-dicarboxylic acids, diphenylethane -4,4 '-dicarboxylic acids, diphenylprop Alkane -4,4 '-dicarboxylic acids, diphenyl ether -4,4 '-dicarboxylic acids, diphenyl sulfone -4,4 '-dicarboxylic acids, 4,4 '-diphenyldicarboxylic acids, 4, Unit derived from the aromatic dicarboxylic acids such as 4 '-triphenyl dicarboxylic acids, they can be used one kind or two or more.These other dicarboxyls The content of acid unit is 50 moles of % hereinafter, preferably 40 moles of % are hereinafter, more preferably 30 relative to whole dicarboxylic acid units Mole % or less.In turn, trimellitic acid, trimesic acid, equal benzene four can also be used in the range of being able to carry out melt-shaping The polybasic carboxylic acids such as acid.
As long as semiaromatic polyamide composition (d2) may include in the range of not damaging each excellent characteristics of gained stacking pipe Other units other than dicarboxylic acid units and diamine unit.As other units, can enumerate by caprolactam, acyl in heptan The unit of the lactam derivatives such as amine, 11 lactams, lauric lactam, alpha-pyrrolidone, α-piperidones；By 6-aminocaprolc acid, The aliphatic amines carboxylic acids such as 7- aminoheptylic acid, 9 aminononanoic acid, 11- amino undecanoic acid, 12 amino dodecanoic acid, to amino Unit derived from the amino carboxylic acid of the aromatic amines yl carboxylic acid such as methyl benzoic acid.They can be used one kind or two or more.It is other The content of unit is on the basis of whole dicarboxylic acid units, preferably 30 moles of % or less, more preferably 10 moles of % or less.
As the manufacturing device of semiaromatic polyamide composition (d2), batch reaction kettle, single-channel type~multi-groove type can be enumerated The mixings such as continuous reaction apparatus, tubulose continuous reaction apparatus, single-bolt type mixing extruder, double-screw type mixing extruder it is anti- Answer polyamide manufacturing device well known to extruder etc..As the manufacturing method of semiaromatic polyamide composition (d2), there is melt polymerization, molten Method well known to liquid polymerization, solid phase etc., can be used these methods, repeat normal pressure, decompression, pressurized operation manufacture Semiaromatic polyamide composition (d2).These manufacturing methods can be used alone or appropriately combined use, preferably molten among these Melt polymerization.For example, by that will be 8 or more and 13 fat below by benzene dimethylamine and/or bis- (amino methyl) naphthalenes and carbon number The nylon salt that race's dicarboxylic acids is formed is pressurizeed in presence of water, is heated up. while remove added water and condensation water In the molten state manufacture the method for its polymerization.In addition it is also possible to by by benzene dimethylamine and/or bis- (amino methyl) naphthalenes The carbon number for being added directly to molten condition is in 8 or more and 13 aliphatic dicarboxylic acids below, and carries out polycondensation under normal pressure Method manufactures.At this point, in order to which reaction system is remained uniform liquid condition, by benzene dimethylamine and/or bis- (amino first Base) naphthalene be continuously added to carbon number be 8 or more and 13 aliphatic dicarboxylic acids below in, therebetween so that the temperature of reaction system is The mode more than fusing point of oligoamide and polyamide generated heats up to reaction system, while promoting polymerization.In addition, Semiaromatic polyamide composition (d2) can be after being manufactured by melt phase polycondensation, then carries out solid phase.
In semiaromatic polyamide composition (d2), as catalyst, or in order to improve processing stability when melt-shaping, be It prevents from colouring, can add phosphorus compound.As phosphorus compound, the alkali salt of hypophosphorous acid, phosphorous acid can be enumerated Alkali metal salt, the alkali salt of phosphorous acid, the alkali metal salt of phosphoric acid, the alkali salt of phosphoric acid, pyrophosphoric acid alkali metal salt, The alkali salt of the alkali salt of pyrophosphoric acid, the alkali metal salt of metaphosphoric acid and metaphosphoric acid.
Specifically, calcium hypophosphite, magnesium hypophosphite, sodium phosphite, hydrogen phosphite sodium, potassium phosphite, phosphorous can be enumerated Potassium hydrogen phthalate, phosphorous acid lithium, hydrogen phosphite lithium, phosphorous acid magnesium, hydrogen phosphite magnesium, Arizona bacilli, calcium phosphite, sodium phosphate, phosphorus Sour disodium hydrogen, sodium dihydrogen phosphate, potassium phosphate, dipotassium hydrogen phosphate, potassium dihydrogen phosphate, magnesium phosphate, two magnesium of phosphoric acid hydrogen, biphosphate Magnesium, calcium phosphate, dicalcium phosphate, calcium dihydrogen phosphate, lithium phosphate, two lithium of phosphoric acid hydrogen, lithium dihydrogen phosphate, sodium pyrophosphate, pyrophosphoric acid Potassium, magnesium pyrophosphate, calcium pyrophosphate, pyrophosphoric acid lithium, sodium metaphosphate, potassium metaphosphate, magnesium metaphosphorate, calcium metaphosphate, lithium metaphosphate etc.. They can be used one kind or two or more.Among these, preferably calcium hypophosphite, magnesium hypophosphite, Arizona bacilli, hydrogen phosphite Calcium, calcium dihydrogen phosphate, more preferably calcium hypophosphite.It should be noted that these phosphorus compounds can be hydrate.
From catalytic effect, the anti-coloring effect when substantially ensuring polymerization, and from the perspective of inhibition gel generation, phosphatization is closed The content of object relative to 100 mass parts of semiaromatic polyamide composition (d2), with phosphorus atom concentration conversion be preferably 0.030 mass parts with It is upper and 0.30 below the mass, more than more preferably 0.050 mass parts and 0.20 below the mass, further preferably 0.070 More than mass parts and 0.15 below the mass.
The adding method of these phosphorus compounds can enumerate: be added to the raw material i.e. nylon salt of semiaromatic polyamide composition (d2) Method in aqueous solution, diamines or dicarboxylic acids；The method added into dicarboxylic acids in a molten state；Add into melt polymerization The method etc. added can be any method, not limit as long as it can be made to be dispersed in semiaromatic polyamide composition (d2) In these.
Alkali metal compound can be added with being applied in combination with phosphorus compound in semiaromatic polyamide composition (d2).In order to prevent Polyamide coloring in polycondensation, needs to have phosphorus compound with substantial amount, but according to circumstances, occasionally there are lead to polyamide Alkali metal compound has further preferably coexisted in order to adjust amidation process speed in the worry of gelation.As alkali metal chemical combination Object can enumerate alkali metal hydroxide, alkaline earth metal hydroxide, alkali metal acetate and alkaline earth metal acetates, preferably For alkali metal hydroxide, alkali metal acetate.
As alkali metal compound, specifically, lithium hydroxide, sodium hydroxide, potassium hydroxide, hydroxide can be enumerated Rubidium, cesium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, lithium acetate, sodium acetate, potassium acetate, rubidium acetate, Cesium acetate, magnesium acetate, calcium acetate, strontium acetate, barium acetate etc..They can be used one kind or two or more.Among these, from economy From the perspective of property, preferably sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, sodium acetate, potassium acetate, preferably hydrogen Sodium oxide molybdena, sodium acetate, potassium acetate.
Into the condensation polymer system of semiaromatic polyamide composition (d2) when addition alkali metal compound, from the rush to amidation process Into from the perspective of the balance with inhibition, the molal quantity of the compound convert molal quantity divided by the phosphorus atoms of aforementioned phosphorus compound and Obtained value is preferably 0.30 or more and 1.0 or less, more preferably 0.40 or more and 0.95 or less, further preferably 0.50 with It is upper and 0.90 or less.
The adding method of these alkali metal compounds can enumerate: be added to the raw material i.e. Buddhist nun of semiaromatic polyamide composition (d2) Method in imperial saline solution, diamines or dicarboxylic acids；The method added into dicarboxylic acids in a molten state；To melt polymerization The method etc. of middle addition can be any method, no as long as it can be made to be dispersed in semiaromatic polyamide composition (d2) It is defined in these.
Ensure to be laminated the reason of pipe from ensuring the engineering properties of gained stacking pipe, making viscosity holding proper range when melting From the perspective of thinking formability, measured under conditions of 96% sulfuric acid, 1%, 25 DEG C of polymer concentration according to JIS K-6920 Semiaromatic polyamide composition (d1), semiaromatic polyamide composition (d2) relative viscosity be preferably 1.5 or more and 4.0 or less, it is more excellent It is selected as 1.8 or more and 3.5 or less, further preferably 2.0 or more and 3.0 or less.
It should be noted that the type of the end group of semiaromatic polyamide composition (d1), semiaromatic polyamide composition (d2) and Its concentration, molecular weight distribution are not particularly limited.In order to molecular weight adjusting, forming when melt stability, Ke Yitian Add monoamine, diamines, polyamines, monocarboxylic acid, a kind among dicarboxylic acids or it is appropriately combined two or more add.Such as it can enumerate The aliphatic such as methylamine, ethamine, propylamine, butylamine, hexylamine, octylame, decyl amine, stearylamine, dimethylamine, diethylamine, di-n-propylamine, dibutyl amine Monoamine；The ester ring types monoamine such as cyclohexylamine, dicyclohexyl amine；The aromatic series monoamine such as aniline, toluidines, diphenylamines, naphthylamines；1,4- fourth two Amine, 1,5- pentanediamine, 1,6- hexamethylene diamine, 1,8- octamethylenediamine, 2- methyl-1, the aliphatic diamines such as 5- pentanediamine；It is cyclohexanediamine, double The ester ring types diamines such as (amino methyl) hexamethylene, 5- amino -1,3,3- trimethyl-cyclohexane methylamine；M-phenylene diamine (MPD), p-phenylenediamine Equal aromatic diamines；The polyamines such as polyalkyleneimine, polyalkylene polyamine, polyvinylamine, polyallylamine；Acetic acid, propionic acid, fourth The fat such as acid, valeric acid, caproic acid, octanoic acid, lauric acid, tridecanoic acid, myristic acid, palmitinic acid, stearic acid, pivalic acid, isobutyric acid Race's monocarboxylic acid；The ester ring types monocarboxylic acid such as cyclohexane-carboxylic acid；Benzoic acid, toluic acid, α-naphthoicacid, β-naphthoic acid, methyl naphthalene first The aromatic monocarboxylates such as acid, phenylacetic acid；The aliphatic dicarboxylic acids such as adipic acid, pimelic acid；1,3- cyclopentane dicarboxylic acid, 1,3- hexamethylene The ester ring types dicarboxylic acids such as alkane dicarboxylic acids, 1,4- cyclohexane dicarboxylic acid；The aromatic dicarboxylic acids such as phthalic acid, M-phthalic acid. They can be used one kind or two or more.The dosage of these molecular weight regulators because molecular weight regulator reactivity, polymerization item Part and it is different, be suitably determined in the way of making the relative viscosity aforementioned range for wanting finally obtained polyamide.
When in view of melt stability, the molecule chain end of semiaromatic polyamide composition (d1), semiaromatic polyamide composition (d2) It is preferably blocked agent sealing end, 10% or more of more preferable end group is blocked, and 20% or more of further preferred end group It is blocked.As end-capping reagent, as long as having and the amino of polyamides amine end or the reactive monofunctional compounds of carboxyl It is just not particularly limited, from viewpoints, preferably monocarboxylic acid or monoamine such as the stability of reactivity, sealing end end, from processing From the perspective of easness etc., more preferably monocarboxylic acid.In addition to this it is possible to use the acid anhydrides such as phthalic anhydride, Dan Yi Cyanate, single carboxylic acid halides, monoesters class, single methanol class etc..
As the monocarboxylic acid for being used as end-capping reagent, it is not particularly limited, can enumerates as long as there is the reactivity with amino Aforementioned aliphatic monocarboxylic acid, ester ring type monocarboxylic acid, aromatic monocarboxylate etc. out.Among these, from reactivity, the steady of end is blocked From the perspective of qualitative, price etc., preferably acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, octanoic acid, lauric acid, tridecanoic acid, meat Myristic acid, palmitinic acid, stearic acid, benzoic acid.As the monoamine for being used as end-capping reagent, do not have as long as there is the reactivity with carboxyl It is particularly limited to, aforementioned aliphatic monoamine, ester ring type monoamine, aromatic series monoamine etc. can be enumerated.Among these, from reactivity, Boiling point, from the perspective of blocking stability, price etc. of end, preferably butylamine, hexylamine, octylame, decyl amine, stearylamine, hexamethylene Amine, aniline.
The dosage of end-capping reagent is contemplated that reactivity, boiling point, reaction unit, reaction condition of used end-capping reagent etc. to fit Work as selection.From the viewpoint of adjusting the degree of polymerization, relative to the total mole number of dicarboxylic acids and diamines as material composition, preferably For 0.1 mole of % or more and 15 mole of % or less.
In semiaromatic polyamide composition composition (D1), semiaromatic polyamide composition composition (D2), containing semiaromatic adoption While amide (d1), semiaromatic polyamide composition (d2), other polyamide resins or other thermoplastic resins can also be contained. As other polyamide resins or other thermoplastic resins, the case where can enumerating with aforementioned fatty polyamide (A), is identical Resin.In turn, it is also possible to and the mixture of fatty polyamide (A).Semiaromatic polyamide composition (d1) in mixture, half The content of aromatic polyamide (d2) is preferably 60 mass % or more.
It in turn, as needed, can also be to semiaromatic polyamide composition composition (D1), semiaromatic polyamide composition composition (D2) in addition antioxidant, heat stabilizer, ultraviolet absorbing agent, Photostabilised dose, lubrication prescription, inanimate matter packing material, resist it is quiet Electric agent, fire retardant, crystallization promoter, plasticizer, colorant, lubricant, modified impact material etc..In order to improve semiaromatic adoption The low-temperature impact resistance of amide (d1), semiaromatic polyamide composition (d2), preferably addition modified impact material, especially, more preferably Add 6 composition of foregoing polyamides (B1), record in polyamide 6/66/12 composition (B2), measure according to ISO 178 it is curved Modulus in elasticity in bending is 500MPa rubber-like polymer below.
(5. e) layer
(e) layer that pipe is laminated includes (E) containing fluorine system polymer, and (E) containing fluorine system polymer is imported in strand There is reactive functional group to amino.
[(E) containing fluorine system polymer that there is reactive functional group to amino has been imported in strand]
(E) containing fluorine system polymer is to have imported to have polymerizeing containing fluorine system for reactive functional group to amino in strand Object (hereinafter sometimes referred to (E) containing fluorine system polymer).
(E) containing fluorine system polymer be have at least one kind of repetitive unit as derived from fluorochemical monomer polymer (homopolymer or Copolymer).As long as be able to carry out heat fusing processing containing being not particularly limited as long as fluorine system polymer.
Herein, as fluorochemical monomer, tetrafluoroethene (TFE), trifluoro-ethylene, vinylidene fluoride (VDF), fluorine second can be enumerated Alkene (VF), chlorotrifluoroethylene (CTFE), trichlorine vinyl fluoride, hexafluoropropene (HFP), CF2=CFORf1(herein, Rf1Indicate that carbon number is 1 or more and 10 it is below optionally include etheric oxygen atom perfluoroalkyls), CF2=CF-OCH2-Rf2(herein, Rf2Indicate carbon number For 1 or more and 10 it is below optionally include etheric oxygen atom perfluorinated alkylidenes), CF2=CF (CF2)pOCF=CF2(herein, p For 1 or 2), CH2=CX1(CF2)nX2(herein, X1And X2Indicate hydrogen atom or fluorine atom independently of one another, n be 2 or more and 10 with Under integer) etc..They can be used one kind or two or more.
As above-mentioned general formula CF2=CFORf1Concrete example, CF can be enumerated2=CFOCF2(perfluor (methyl vinyl ether): PMVE)、CF2=CFOCF2CF3(perfluor (ethyl vinyl ether): PEVE), CF2=CFOCF2CF2CF3(perfluor (propyl ethylene base Ether): PPVE), CF2=CFOCF2CF2CF2CF3(perfluor (butyl vinyl ether): PBVE), CF2=CFO (CF2)8(perfluor is (pungent by F Base vinyl ethers): POVE) perfluors (alkyl vinyl ether) (hereinafter sometimes referred to PAVE) such as.Among these, preferably CF2= CFOCF2、CF2=CFOCF2CF2CF3。
In addition, (such as inhibiting to produce when forming in copolymer and/or in formed products from the modification ensured containing fluorine system polymer Raw crackle) effect, obtain sufficient polymerisation reactivity from the perspective of, above-mentioned general formula CH2=CX1(CF2)nX2(herein, X1And X2 Indicating that hydrogen atom or fluorine atom, n are 2 or more and 10 integers below independently of one another) n in compound represented is 2 or more And 10 integer below.Specifically, CH can be enumerated2=CF (CF2)2F、CH2=CF (CF2)3F、CH2=CF (CF2)4F、CH2 =CF (CF2)5F、CH2=CF (CF2)8F、CH2=CF (CF2)2H、CH2=CF (CF2)3H、CH2=CF (CF2)4H、CH2=CF (CF2)5H、CH2=CF (CF2)8H、CH2=CH (CF2)2F、CH2=CH (CF2)3F、CH2=CH (CF2)4F、CH2=CH (CF2)5F、 CH2=CH (CF2)8F、CH2=CH (CF2)2H、CH2=CH (CF2)3H、CH2=CH (CF2)4H、CH2=CH (CF2)5H、CH2=CH (CF2)8H etc..They can be used one kind or two or more.
Among these, from the balance of anti-chemical solution permeability and environmental stress resistance cracking containing fluorine system polymer (E) From the perspective of, preferably CH2=CH (CF2)nF or CH2=CF (CF2)nH compound represented, the n in formula be more preferably 2 with It is upper and 4 or less.
Containing in fluorine system polymer (E), other than above-mentioned fluorochemical monomer, can also further contain based on not fluorochemical monomer Polymerized unit.As not fluorochemical monomer, can enumerate the carbon numbers such as ethylene, propylene, isobutene is 2 or more and 4 alkene below； Vinyl chloride, vinylidene chloride, vinyl acetate, vinyl chloroacetate, lactate, vinyl butyrate, pivalic acid vinyl acetate, Vinyl benzoate, Vinyl crotonate, (methyl) methyl acrylate, (methyl) ethyl acrylate, the positive fourth of (methyl) acrylic acid The vinyl acetates such as ester, ethyl crotonate；Methyl vinyl ether (MVE), ethyl vinyl ether (EVE), butyl vinyl ether (BVE), Vinyl ethers such as isobutyl vinyl ether (IBVE), cyclohexyl vinyl ether (CHVE), glycidyl vinyl ether etc..They It can be used one kind or two or more.Among these, preferably ethylene, propylene, vinyl acetate, more preferably ethylene.
Among fluorine system polymer (E), go out from the viewpoint of heat resistance, chemical reagent resistance and anti-chemical solution permeability Hair, the preferably at least copolymer (E1) comprising vinylidene fluoride units (VDF unit) include at least tetrafluoroethylene units (TFE Unit) and ethylene unit (E unit) copolymer (E2), include at least tetrafluoroethylene units (TFE unit) and hexafluoropropene list First (HFP unit) and/or it is originated from above-mentioned general formula CF2=CFORf1(herein, Rf1Expression carbon number is 1 or more and 10 optional packets below Perfluoroalkyl containing etheric oxygen atom) shown in PAVE PAVE unit copolymer (E3), include at least chlorotrifluoroethylene list The copolymer (E4) of first (CTFE unit), including at least chlorotrifluoroethylene unit (CTFE unit) and tetrafluoroethylene units, (TFE is mono- Member) copolymer (E5).
As copolymer (E1) (the hereinafter sometimes referred to VDF copolymer for including at least vinylidene fluoride units (VDF unit) (E1)) it, such as can enumerate:
Foraflon (polyvinylidene fluoride (PVDF)) (E1-1)；
Copolymer (E1-2) is the copolymer comprising VDF unit and TFE unit, contains functional group relative in addition to aftermentioned Monomer except monomer it is whole, the content of VDF unit is 30 moles of % or more and 99 mole of % or less and TFE unit Content is 1 mole of % or more and 70 mole of % or less；
Copolymer (E1-3) is the copolymer comprising VDF unit, TFE unit and trichlorine vinyl fluoride unit, relative to removing Monomer except the aftermentioned monomer containing functional group is whole, the content of VDF unit be 10 moles of % or more and 90 mole of % or less, The content of TFE unit be 0 mole of % or more and 90 mole of % or less and the content of trichlorine vinyl fluoride unit be 0 mole of % with Upper and 30 moles of % or less；
Copolymer (E1-4) is the copolymer comprising VDF unit, TFE unit and HFP unit, relative in addition to aftermentioned Monomer except monomer containing functional group is whole, and the content of VDF unit is that 10 moles of % or more and 90 mole of % or less, TFE are mono- The content of member is 0 mole of % or more and 90 mole of % or less and the content of HFP unit is 0 mole of % or more and 30 mole of % Below；Deng.
It is whole relative to the monomer other than the aftermentioned monomer containing functional group in above-mentioned copolymer (E1-4), preferably It is that the content of VDF unit is 15 moles of % or more and 84 mole of % or less, the content of TFE unit is 15 moles of % or more and 84 The content of mole % or less and HFP unit is 0 mole of % or more and 30 mole of % or less.
(have below as the copolymer (E2) for including at least tetrafluoroethylene units (TFE unit) and ethylene unit (E unit) When referred to as TFE copolymer (E2)), such as can enumerate: it is whole relative to the monomer other than the aftermentioned monomer containing functional group, The content of TFE unit is the polymer of 20 moles of % or more, and then can enumerate: relative in addition to the aftermentioned monomer containing functional group Except monomer it is whole, the content of TFE unit is 20 moles of % or more and 80 mole of % or less, the content of E unit is 20 to rub The content of % or more and 80 mole of % or less of that and the unit from the monomer that can be copolymerized with them is 0 mole of % or more And 60 moles of % copolymers below etc..
As the above-mentioned monomer that can be copolymerized, hexafluoropropene (HFP), above-mentioned general formula CF can be enumerated2=CFORf1(herein, Rf1Indicate carbon number be 1 or more and 10 it is below optionally include etheric oxygen atom perfluoroalkyls), above-mentioned general formula CH2=CX1 (CF2)nX2(herein, X1And X2Indicate that hydrogen atom or fluorine atom, n are 2 or more and 10 integers below independently of one another.) etc..It Can be used it is one kind or two or more.
As TFE copolymer (E2), such as can enumerate:
Copolymer (E2-1) is comprising TFE unit and E unit and to be originated from above-mentioned general formula CH2=CX1(CF2)nX2(this Place, X1And X2Indicate that hydrogen atom or fluorine atom, n are 2 or more and 10 integers below independently of one another) shown in fluoroolefin The copolymer of fluoroolefin unit, the content of TFE unit whole relative to the monomer other than the aftermentioned monomer containing functional group Content for 30 moles of % or more and 70 mole of % or less, E unit is 20 moles of % or more and 55 mole of % or less and is originated from Above-mentioned general formula CH2=CX3(CF2)nX4(herein, X3And X4Indicate hydrogen atom or fluorine atom independently of one another, n be 2 or more and 10 with Under integer) shown in fluoroolefin fluoroolefin unit content be 0 mole of % or more and 10 mole of % or less；
Copolymer (E2-2) is comprising TFE unit and E unit and HFP unit and from can be copolymerized with them The copolymer of the unit of monomer, whole relative to the monomer other than the aftermentioned monomer containing functional group, the content of TFE unit is 30 moles of % or more and 70 mole of % or less, E unit content be 20 moles of % or more and 55 mole of % or less, HFP unit Content is 1 mole of % or more and 30 mole of % or less and the content of the unit from the monomer that can be copolymerized with them be 0 to rub You are % or more and 10 mole of % or less；
Copolymer (E2-3) is comprising TFE unit and E unit and to be originated from above-mentioned general formula CF2=CFORf1(herein, Rf1Indicate carbon number be 1 or more and 10 it is below optionally include etheric oxygen atom perfluoroalkyls) shown in PAVE PAVE unit Copolymer, it is whole relative to the monomer other than the aftermentioned monomer containing functional group, the content of TFE unit be 30 moles of % with Above and the content of 70 moles of % or less, E unit are 20 moles of % or more and 55 mole of % or less and are originated from above-mentioned general formula CF2 =CFORf1(herein, Rf1Indicate that carbon number is 1 or more and 10 below optionally comprising the perfluoroalkyl of etheric oxygen atom) shown in The content of the PAVE unit of PAVE is 0 mole of % or more and 10 mole of % or less；Deng.
As including at least tetrafluoroethylene units (TFE unit) and hexafluoropropene unit (HFP unit) and/or from above-mentioned General formula CF2=CFORf1(herein, Rf1Indicate that carbon number is 1 or more and 10 below optionally comprising the perfluoroalkyl of etheric oxygen atom) The copolymer (E3) (hereinafter sometimes referred to TFE copolymer (E3)) of the PAVE unit of shown PAVE, such as can enumerate:
Copolymer (E3-1) is the copolymer comprising TFE unit and HFP unit, contains functional group relative in addition to aftermentioned Monomer except monomer it is whole, the content of TFE unit is 70 moles of % or more and 95 mole of % or less, preferably 85 moles of % Above and 93 moles of % are hereinafter, the content of HFP unit is 5 moles of % or more and 30 mole of % or less, preferably 7 moles of % or more And 15 moles of % or less；
Copolymer (E3-2) is comprising TFE unit and to be originated from above-mentioned general formula CF2=CFORf1(herein, Rf1Indicate carbon number For 1 or more and 10 it is below optionally include etheric oxygen atom perfluoroalkyls) shown in PAVE one kind or two or more PAVE it is mono- The copolymer of member, whole relative to the monomer other than the aftermentioned monomer containing functional group, the content of TFE unit is 70 moles of % Above and 95 moles of % or less and be originated from above-mentioned general formula CF2=CFORf1(herein, Rf1Indicate that carbon number is 1 or more and 10 or less Optionally include etheric oxygen atom perfluoroalkyl) shown in the content of one kind or two or more PAVE unit of PAVE be 5 to rub You are % or more and 30 mole of % or less；
Copolymer (E3-3) is comprising by TFE unit and HFP unit and from above-mentioned general formula CF2=CFORf1(this Place, Rf1Indicate carbon number be 1 or more and 10 it is below optionally include etheric oxygen atom perfluoroalkyls) shown in a kind or 2 kinds of PAVE The copolymer of above PAVE unit, whole relative to the monomer other than the aftermentioned monomer containing functional group, TFE unit contains It measures as 70 moles of % or more and 95 mole of % or less, HFP unit and is originated from above-mentioned general formula CF2=CFORf1(herein, Rf1Indicate carbon Number for 1 or more and 10 it is below optionally include etheric oxygen atom perfluoroalkyls) shown in PAVE one kind or two or more PAVE The total content of unit is 5 moles of % or more and 30 mole of % or less；Deng.
Refer to including at least the copolymer of chlorotrifluoroethylene unit (CTFE unit): there is CTFE unit [- CFCl- CF2], the chlorotrifluoroethylene (E4) being made of ethylene unit (E unit) and/or fluorine-containing monomer unit is (following to be sometimes referred to as For CTFE copolymer (E4)).
As the fluorochemical monomer in above-mentioned CTFE copolymer (E4), without special as long as the monomer other than CTFE It limits, vinylidene fluoride (VDF), hexafluoropropene (HFP), above-mentioned general formula CF can be enumerated2=CFORf1(herein, Rf1Indicate carbon number For 1 or more and 10 it is below optionally include etheric oxygen atom perfluoroalkyls) shown in PAVE, above-mentioned general formula CH2=CX1 (CF2)nX2(herein, X1And X2Indicate that hydrogen atom or fluorine atom, n are 2 or more and 10 integers below independently of one another.) shown in Fluoroolefin etc..They can be used one kind or two or more.
It as CTFE copolymer (E4), is not particularly limited, such as CTFE/PAVE copolymer, CTFE/VDF can be enumerated Copolymer, CTFE/HFP copolymer, CTFE/E copolymer, CTFE/PAVE/E copolymer, CTFE/VDF/E copolymer, CTFE/ HFP/E copolymer etc..
It is whole relative to the monomer other than the aftermentioned monomer containing functional group, the CTFE unit in CTFE copolymer (E4) Content be preferably 15 moles of % or more and 70 mole of % or less, more preferably 18 moles of % or more and 65 mole of % or less.Separately On the one hand, the content of E unit and/or fluorine-containing monomer unit is preferably 30 moles of % or more and 85 mole of % or less, is more preferably 35 moles of % or more and 82 mole of % or less.
Copolymer (E5) including at least chlorotrifluoroethylene unit (CTFE unit) and tetrafluoroethylene units (TFE unit) is By CTFE unit [- CFCl-CF2] and TFE unit [- CF2-CF2] and can be with the monomeric unit structure of CTFE and TFE copolymerization At chlorotrifluoroethylene (hereinafter sometimes referred to CTFE/TFE copolymer (E5)).
As the monomer that can be copolymerized in above-mentioned CTFE/TFE copolymer (E5), as long as other than CTFE and TFE Monomer, there is no particular limitation, vinylidene fluoride (VDF), hexafluoropropene (HFP), above-mentioned general formula CF can be enumerated2= CFORf1(herein, Rf1Indicate that carbon number is 1 or more and 10 below optionally comprising the perfluoroalkyl of etheric oxygen atom) shown in PAVE, above-mentioned general formula CH2=CX1(CF2)nX2(herein, X1And X2Indicate that hydrogen atom or fluorine atom, n are 2 or more independently of one another And 10 integers below) shown in the fluorochemical monomers such as fluoroolefin；The carbon numbers such as ethylene, propylene, isobutene are 2 or more and 4 or less The vinyl acetates, methyl vinyl ether such as alkene, vinyl acetate, (methyl) methyl acrylate, (methyl) ethyl acrylate (MVE), the not fluorochemical monomer such as vinyl ethers such as ethyl vinyl ether (EVE), butyl vinyl ether (BVE).They can be used 1 Kind or two or more.Among these, preferably above-mentioned general formula CF2=CFORf1(herein, Rf1Indicate that carbon number is 1 or more and 10 or less Optionally include etheric oxygen atom perfluoroalkyl) shown in PAVE, more preferably perfluor (methyl vinyl ether) (PMVE), complete Fluorine (propyl vinyl ether) (PPVE), from the viewpoint of heat resistance, further preferably PPVE.
It as CTFE/TFE copolymer (E5), is not particularly limited, such as CTFE/TFE copolymer, CTFE/ can be enumerated TFE/HFP copolymer, CTFE/TFE/VDF copolymer, CTFE/TFE/PAVE copolymer, CTFE/TFE/E copolymer, CTFE/ TFE/HFP/PAVE copolymer, CTFE/TFE/VDF/PAVE copolymer etc., among these, preferably CTFE/TFE/PAVE copolymerization Object, CTFE/TFE/HFP/PAVE copolymer.
From ensuring good formability, environmental stress resistance cracking, anti-chemical solution permeability, heat resistance and mechanical property From the perspective of, it is whole relative to the monomer other than the aftermentioned monomer containing functional group, in CTFE/TFE copolymer (E5) The total content of CTFE unit and TFE unit is preferably 90.0 moles of % or more and 99.9 mole of % hereinafter, can be with above-mentioned CTFE Content with the monomeric unit of TFE copolymerization is preferably 0.10 mole of % or more and 10.0 mole of % or less.
From the viewpoint of ensuring good formability, environmental stress resistance cracking and anti-chemical solution permeability, relatively The content of CTFE unit in 100 moles of % of total amount of above-mentioned CTFE unit and TFE unit, CTFE/TFE copolymer (E5) Preferably 15 moles of % or more and 80 mole of % or less, 17 moles of % or more and 70 mole of % or less are more preferably, is further excellent It is selected as 19 moles of % or more and 65 mole of % or less.
In CTFE/TFE copolymer (E5), when the monomer that can be copolymerized with above-mentioned CTFE and TFE is PAVE, relative in addition to Monomer except the aftermentioned monomer containing functional group is whole, the content of PAVE unit be preferably 0.5 mole of % or more and 7 mole of % with Under, more preferably 1 mole of % or more and 5 mole of % or less.
In CTFE/TFE copolymer (E5), when the monomer that can be copolymerized with above-mentioned CTFE and TFE is HFP and PAVE, relatively Whole in the monomer other than the aftermentioned monomer containing functional group, the total content of HFP unit and PAVE unit is preferably 0.5 to rub You are % or more and 7 mole of % or less, more preferably 1 mole of % or more and 5 mole of % or less.
The anti-chemical solution permeability, outstanding of TFE copolymer (E3), CTFE copolymer (E4), CTFE/TFE copolymer (E5) It is very excellent for the barrier property of alcohol blended fuel.Alcohol blended fuel transmission coefficient refers to: to investment have by isooctane, toluene and In the isooctane that ethyl alcohol is mixed to get with the volumetric ratio of 45:45:10/toluene/ethanol mixed solvent transmission coefficient measurement cup It is put into the piece obtained by measure object resin, and the value calculated according to the mass change measured at 60 DEG C.TFE copolymer (E3), CTFE copolymer (E4), CTFE/TFE copolymer (E5) above-mentioned alcohol blended fuel transmission coefficient be preferably 1.5gmm/ (m2Day) below, more preferably 0.010gmm/ (m2Day more than) and 1.0gmm/ (m2Day) below, further Preferably 0.020gmm/ (m2Day more than) and 0.80gmm/ (m2Day) below.
It can be by the way that the monomer for constituting polymer be polymerize (copolymerization) with previous polymerization containing fluorine system polymer (E) To obtain.Wherein, the method based on free radical polymerization is mainly used.That is, in order to cause polymerization, as long as based on free radical come into Row does not then have an any restrictions to means, for example, by organic free radical polymerization initiator, Inorganic radicals polymerization initiator, heat, Light or ionization radial line etc. cause.
Manufacturing method containing fluorine system polymer (E) is not particularly limited, and usually used utilization radical polymerization can be used Close the polymerization of initiator.As polymerization, bulk polymerization can be used, use fluorohydrocarbon, chlorohydrocarbon, fluoro chloro The polymerisation in solution of the organic solvents such as hydrocarbon, alcohol, hydrocarbon；It is using aqueous medium and poly- using the suspension of organic solvent appropriate as needed It closes；Method well known to emulsion polymerization using aqueous medium and emulsifier etc..
In addition, stirred type polyplant, the cast polyplant of single slot~multi-groove type can be used in polymerization, with intermittent or The form of continous way operation is implemented.
As radical polymerization initiator, preferably half-life period be 10 hours decomposition temperature be 0 DEG C or more and 100 DEG C with Under, more preferably 20 DEG C or more and 90 DEG C or less.As concrete example, 2,2 '-azobis isobutyronitriles, 2,2 '-azos can be enumerated Bis- (2,4- methyl pentane nitriles), 2,2 '-azos bis- (2- methyl valeronitriles), 2,2 '-azos bis- (2- cyclopropyl propionitrile), 2,2 '-are occasionally The double isobutyl dimethyl phthalates of nitrogen, 2,2 '-azos bis- [2- (hydroxymethyl) propionitrile], 4,4 '-azos bis- (4- cyano penetenoic acids) etc. are even Nitrogen compound；The hydrogen peroxide such as hydrogen peroxide, tert-butyl hydroperoxide, isopropyl benzene hydroperoxide；Di-tert-butyl peroxide, two The dialkyl peroxides such as cumyl peroxide；Acetyl peroxide, isobutyryl peroxide, caprylyl peroxide, benzoyl peroxide, The non-fluorine system peroxidating two acyl such as lauroyl peroxide；The ketone peroxides such as methyl ethyl ketone peroxide, cyclohexanone peroxide；Diisopropyl mistake Aoxidize the peroxy dicarbonates such as two carbonic esters；T-butylperoxy-valerate, tert-butyl hydroperoxide isobutyrate, tert-butyl mistake The peroxyesters such as acetic oxide ester；(Z(CF2)pCOO)2(herein, Z is hydrogen atom, fluorine atom or chlorine atom, and p is 1 or more and 10 Integer below) the fluorine-containing peroxidating two acyl such as compound represented；The inorganic peroxies such as potassium peroxydisulfate, sodium peroxydisulfate, ammonium persulfate Compound etc..They can be used one kind or two or more.
In addition, in order to adjust molecular weight, further preferably using common chain-transferring agent when manufacture is containing fluorine system polymer (E).Make For chain-transferring agent, the alcohol such as methanol, ethyl alcohol can be enumerated；The chloro- 1,1,2,2,3- pentafluoropropane of 1,3- bis-, the chloro- 1- fluorine second of 1,1- bis- The chlorine such as alkane, the chloro- 1,1,2,2- tetrafluoroethane of 1,2- bis-, the chloro- 1- fluoroethane of 1,1- bis-, the chloro- 1,2,2- trifluoroethane of 1,1,2- tri- Fluorohydrocarbon；The hydrocarbon such as pentane, hexane, hexamethylene；The chlorohydrocarbons such as carbon tetrachloride, chloroform, methylene chloride, chloromethanes.They can be used 1 Kind or two or more.
Polymerizing condition is not particularly limited, polymerization temperature is preferably 0 DEG C or more and 100 DEG C or less, more preferably 20 DEG C Above and 90 DEG C or less.In order to avoid causing heat resistance to reduce because generating ethylene-vinyl chain in polymer, it is often preferred that low Temperature.Polymerization pressure is suitably determined according to other polymerizing conditions such as used solvent type, amount, vapour pressure, polymerization temperatures, excellent It is selected as 0.1MPa or more and 10MPa or less, more preferably 0.5MPa or more and 3MPa or less.Polymerization time be preferably 1 hour with It is upper and 30 hours or less.
In addition, the molecular weight containing fluorine system polymer (E) is not particularly limited, it is preferably the polymer of solid at room temperature, And its own can come in the form of thermoplastic resin, elastomer etc. using.In addition, molecular weight is dense according to the monomer that polymerization uses Degree, the concentration of polymerization initiator, the concentration of chain-transferring agent, temperature control.
Fluorine system polymer (E) and aforementioned fatty polyamide (A), polyamide 6 composition (B1), polyamide 6/66/ will be contained 12 compositions (B2), EVOH (C), semiaromatic polyamide composition composition (D1), semiaromatic polyamide composition composition (D2) etc. carry out When coextrusion, in order to ensure in the melting temperature significantly deteriorated that will not bring them and within the scope of forming temperature adequately to melt Mobility, the melt flow rate (MFR) at high 50 DEG C of the temperature of fusing point than containing fluorine system polymer (E) and 5kg load are preferably 0.5g/10 minutes or more and 200g/10 minutes or less, more preferably 1g/10 minutes or more and 100g/10 minutes or less.
In addition, can be adjusted by type, ratio of components of selection fluorochemical monomer and other monomers etc. containing fluorine system polymer (E) Fusing point, the glass transition temperature of polymer.
Fusing point containing fluorine system polymer (E) is suitably selected according to purpose, purposes, application method, with aforementioned aliphatic Polyamide (A), polyamide 6 composition (B1), polyamide 6/66/12 composition (B2), EVOH (C), semiaromatic polyamide composition group When conjunction object (D1), semiaromatic polyamide composition composition (D2) etc. are coextruded, it is preferably close to the forming temperature of the resin.Cause This, the preferred ratio of the aforementioned fluorochemical monomer of appropriate adjustment, other monomers and the aftermentioned monomer containing functional group makes containing fluorine system polymer (E) fusing point reaches best.Especially from substantially ensure with EVOH (C) be coextruded when hot-melt stability, progressive forming, From the perspective of heat resistance, chemical reagent resistance and anti-chemical solution permeability containing fluorine system polymer (E), this contains fluorine system polymerization The fusing point of object (E) is preferably 150 DEG C or more and 280 DEG C or less.
Herein, fusing point refers to, using differential scanning calorimetry measurement device, sample is heated to the temperature of the fusing point of anticipation or more Degree, then, which is cooled down with every 1 minute 10 DEG C of speed, is cooled to 30 DEG C, and the state is kept to place about 1 minute Afterwards, it is heated up with every 1 minute 10 DEG C of speed, the peak temperature of the fusion curve thus measured is defined as fusing point.
For (E) containing fluorine system polymer comprising having reactive functional group to amino in molecular structure, functional group can also be with It include the molecular end containing fluorine system polymer (E) or any place in side chain or main chain.In addition, functional group polymerize containing fluorine system It can be used alone, or be applied in combination two or more in object (E).The type of the functional group, content are according to being layered in containing fluorine system The type of subject material on polymer (E), shape, purposes, the adhesiveness between layers of requirement, adhering method, importing side, functional group Method etc. is suitably determined.
As to amino have reactive functional group, can enumerate select free carboxyl group, anhydride group or carboxylate, sulfo group or It is at least one kind of in the group that sulfonate, epoxy group, cyano, carbonate group and haloformyl form.Among these, preferably select It is at least one kind of in the group that free carboxyl group, anhydride group or carboxylate, epoxy group, carbonate group and haloformyl form.
As to containing the method with reactive functional group is imported in fluorine system polymer (E), can enumerate: (i) is containing When the polymerization of fluorine system polymer (E), method that the monomer that can be copolymerized with functional group is copolymerized；(ii) pass through polymerization Initiator, chain-transferring agent etc., in the method that the molecular end of polymerization Shi Xianghan fluorine system polymer (E) imports functional group；(iii) make Have the compound (graft compound) with reactive functional group He the functional group for capableing of grafting graft to it is poly- containing fluorine system Close the method etc. in object.These introduction methods can be used alone or appropriately combined use.In view of the interlayer of stacking pipe is viscous When connecing property, preferably by above-mentioned (i), (E) containing fluorine system polymer of (ii) manufacture.About (iii), it is expected that referring to Japanese Unexamined Patent Publication 7-18035 bulletin, Japanese Unexamined Patent Publication 7-25952 bulletin, Japanese Unexamined Patent Publication 7-25954 bulletin, Japanese Unexamined Patent Publication 7- No. 173230 bulletins, Japanese Unexamined Patent Publication 7-173446 bulletin, Japanese Unexamined Patent Publication 7-173447 bulletin, Japanese Kohyo 10- Manufacturing method described in No. 503236 bulletins.Hereinafter, for (i) in the polymerization containing fluorine system polymer, it will be with functional group The method that the monomer that can be copolymerized is copolymerized；(ii) it by polymerization initiator etc., is led to the molecular end containing fluorine system polymer The method for entering functional group is illustrated.
When (i) manufacture is containing fluorine system polymer (E), the monomer that can be copolymerized with functional group (is write a Chinese character in simplified form sometimes below For the monomer containing functional group) in the method that is copolymerized, will containing select free carboxyl group, anhydride group or carboxylate, hydroxyl, sulfo group or The monomer of the functional group of at least one or more in the group of sulfonate, epoxy group and cyano composition is used as polymerized monomer.As containing official The monomer that can be rolled into a ball, can enumerate the not fluorochemical monomer containing functional group, fluorochemical monomer containing functional group etc..
As the not fluorochemical monomer containing functional group, acrylic acid, haloacrylic acid (wherein not including fluorine), methyl can be enumerated Acrylic acid, halogenated methyl acrylic acid (wherein not including fluorine), maleic acid, halogenated maleic acids (wherein not including fluorine), fumaric acid, halogen For fumaric acid (wherein not including fluorine), itaconic acid, citraconic acid, crotonic acid, bridge-it is bicyclic-[2.2.1] -5- heptene -2,3- dicarboxylic acids The derivatives such as equal unsaturated carboxylic acids, its ester；Maleic anhydride, itaconic anhydride, succinic anhydride, citraconic anhydride, bridge-be bicyclic- The carboxyl group-containing monomers such as [2.2.1] -5- heptene -2,3- dicarboxylic anhydride；Glycidyl acrylate, methyl propenoic acid glycidyl Ester, glycidol ether etc. are containing epoxy based monomers etc..They can be used one kind or two or more.Not fluorochemical monomer containing functional group can Its copolyreaction with the fluorochemical monomer used is considered to determine.By selecting the not fluorochemical monomer appropriate containing functional group, Polymerization can carry out well, be easy equably to be directed into the main chain of the not fluorochemical monomer containing functional group, as a result, in the presence of not anti- It answers monomer to tail off, the advantages of impurity can be reduced.
As the fluorochemical monomer containing functional group, general formula CX can be enumerated3=CX4-(R7)n- Y (herein, Y indicate selected from by- COOM (M indicates hydrogen atom or alkali metal), group ,-SO from carboxyl3M (M indicates hydrogen atom or alkali metal), it is originated from sulfonic acid Group, epoxy group and-CN composition group in functional group, X3And X4It is identical or different, indicate hydrogen atom or fluorine atom (wherein, X3And X4When being hydrogen atom, n=1, R7Include fluorine atom), R7Indicate that carbon number is 1 or more and 40 alkylidenes below, carbon number is 1 or more and 40 fluorine-containing oxyalkylenes below, the carbon number with ehter bond are 1 or more and 40 fluorine-containing alkylidenes or tool below The carbon number for having ehter bond is 1 or more and 40 fluorine-containing oxyalkylenes below, n be 0 or 1) shown in unsaturated compound etc..
For the group from carboxyl as the Y in above-mentioned general formula, such as general formula-C (=O) Q can be enumerated1(in formula, Q1Expression-OR8、-NH2, F, Cl, Br or I, R8Indicate carbon number be 1 or more and 20 alkyl or carbon number below be 6 or more and 22 with Under aryl) shown in group etc..
For the group from sulfonic acid as the Y in above-mentioned general formula, such as general formula-SO can be enumerated2Q2(in formula, Q2Table Show-OR9、-NH2, F, Cl, Br or I, R9Indicate that carbon number is that 1 or more and 20 alkyl or carbon number below are 6 or more and 22 is below Aryl) shown in group etc..
Aforementioned Y is preferably-COOH ,-SO3H、-SO3Na、-SO2F or-CN.
As the fluorochemical monomer containing functional group, for example, with carbonyl functional group when, can enumerate perfluoroacryloyl fluiride, 1- fluoropropene acyl fluorides, propylene acyl fluorides, 1- trifluoromethyl propylene acyl fluorides, perfluorobuttene acid etc..They can be used a kind or 2 kinds with On.
From sufficient adhesiveness between layers are ensured, adhesiveness between layers will not be caused to reduce because of use environment condition, sufficiently really Heat resistance is protected, poor attachment, coloring, foaming occur when preventing from processing at high temperature, when preventing from using at high temperature due to decomposition From the perspective of peeling-off, coloring/foaming, dissolution etc., the content phase containing the monomer containing functional group in fluorine system polymer (E) It is preferably 0.05 mole of % or more and 20 mole of % or less, more preferably 0.05 mole of % or more and 10 for whole polymerized units Mole % or less, further preferably 0.1 mole of % or more and 5 mole of % or less.Before the content of monomer containing functional group is in When stating range, polymerization speed when manufacture will not be reduced, and contain the cementability of fluorine system polymer (E) and the subject material to be laminated It is excellent.The adding method of monomer containing functional group is not particularly limited, and can add together when polymerizeing and starting, can also be poly- It is continuously added in conjunction.Adding method is suitably selected according to the decomposition reaction and polymerization temperature of polymerization initiator, it is preferred that In polymerization, as the monomer containing functional group is consumed because of polymerization, continuously or intermittently into polymerization tank consumed by supply Amount, and the concentration of the monomer containing functional group is maintained into the range.
In addition, can be to be imported with containing fluorine system polymer and not importing for functional group in the case where meeting above-mentioned content The mixture containing fluorine system polymer of functional group.
In the method that (ii) imports functional group to the molecular end containing fluorine system polymer by polymerization initiator etc., function Group is fed to the single end or two ends of the strand containing fluorine system polymer.It is excellent as the functional group for being directed into end It is selected as carbonate group, haloformyl.
The carbonate group imported as the end group containing fluorine system polymer (E) is usually to have-OC (=O) O- key Group, specifically, being-OC (=O) O-R10Base [R10It is hydrogen atom, organic group (for example, carbon number is 1 or more and 20 or less Alkyl, carbon number with ehter bond be 2 or more and 20 alkyl below etc.) or I, II, VII race element] structure, can arrange Enumerate-OC (=O) OCH3,-OC (=O) OC3H7,-OC (=O) OC8H17,-OC (=O) OCH2CH2OCH2CH3Deng.Halogenated formyl The structure of base specifically-COZ [Z is halogens], can enumerate-COF ,-COCl etc..They can be used a kind or 2 kinds More than.
In addition, can use and polymerization initiator, chain has been used to turn to import carbonate group to the molecular end of polymer The various methods for moving agent are preferably used from the viewpoint of the performances such as economy, heat resistance, chemical reagent resistance by peroxide Compound, especially peroxycarbonates, peroxyester are used as the method for polymerization initiator.According to this method, can will be originated from The carbonyl of oxide, the carbonate group for example originating from peroxycarbonates, the ester group from peroxyester or by these functions Haloformyl obtained from group's conversion etc. is directed into polymer ends.It is poly- due to can reduce among these polymerization initiators Temperature is closed, and initiation reaction is not accompanied by side reaction, therefore more preferably uses peroxycarbonates.
In order to import haloformyl to the molecular end of polymer, various methods can be used, for example, can be by end The carbonate group containing fluorine system polymer with aforementioned carbonate group heats and its is made to thermally decompose (decarburization acid), thus obtains.
As peroxycarbonates, diisopropyl peroxycarbonates, diη-propyl peroxycarbonates, uncle can be enumerated Butyl peroxy butylperoxyisopropyl carbonate, tert-butyl hydroperoxide methacryloxyethyl carbonic ester, bis- (4- t-butylcyclohexyls Base) peroxy dicarbonate, two -2- ethylhexyl peroxy dicarbonates etc..They can be used one kind or two or more.
The dosage of peroxycarbonates according to the type of subject polymer (composition etc.), molecular weight, polymerizing condition, use The type of initiator and it is different, from the viewpoint of suitable control polymerization speed, ensure sufficient polymerization speed, relative to because polymerization Obtained from 100 mass parts of whole polymer, more than preferably 0.05 mass parts and 20 below the mass, more preferably 0.1 matter Measure part or more and 10 below the mass.The carbonate group content of the molecular end of polymer can be controlled by adjusting polymerizing condition System.The adding method of polymerization initiator is not particularly limited, and can add, can also connect in polymerization together when polymerizeing and starting Continuous addition.Adding method is suitably selected according to the decomposition reaction and polymerization temperature of polymerization initiator.
From sufficient adhesiveness between layers are ensured, adhesiveness between layers will not be caused to reduce because of use environment condition, sufficiently really Heat resistance is protected, poor attachment, coloring, foaming occur when preventing from processing at high temperature, when preventing from using at high temperature due to decomposition From the perspective of peeling-off, coloring/foaming, dissolution etc., containing in fluorine system polymer (E) relative to main chain carbon number 106A Functional end-group number is preferably 150 or more and 3,000 or less, more preferably 200 or more and 2,000 or less, into one Step preferably 300 or more and 1,000 or less.In addition, can be and be imported in the case where meeting above-mentioned number of functional groups Functional group containing fluorine system polymer and do not import the mixture containing fluorine system polymer of functional group.
As above, (E) containing fluorine system polymer is to be imported with to have polymerizeing containing fluorine system for reactive functional group to amino Object.As described above, (E) containing fluorine system polymer for being imported with functional group be able to maintain that its own, containing fluorine system polymer it is distinctive resistance to The excellent characteristics such as hot, water resistance, low frictional properties, chemical reagent resistance, weatherability, soil resistance, anti-chemical solution permeability, It is advantageous in terms of productivity, cost.
In turn, by, containing there is reactive functional group to amino, in stacking pipe, being glued for interlayer in strand Connecing property is insufficient or a variety of materials that can not be bonded, can directly assign its excellent adhesiveness between layers with other substrates without into Especially processing, the covering of adhesive resin etc. such as row surface treatment.
Containing in fluorine system polymer (E), according to purpose, purposes, in the range of not damaging its performance, inanimate matter can be added The various fillers such as powder, glass fibre, carbon fiber, metal oxide or carbon.In addition, can be mixed other than filler Close pigment, ultraviolet absorbing agent, other arbitrary additives.Other than additive, other fluorine resins, heat can also be added The resins such as plastic resin, synthetic rubber etc., can improve mechanical property, improve weatherability, assign appearance design, it is antistatic, Improve formability etc..
[stacking pipe]
The first method of stacking pipe includes (a) layer comprising fatty polyamide (A), comprising polyamide 6 composition (B1) And/or polyamide 6/66/12 composition (B2) (b) layer, comprising EVOH (C) (c) layer and include semiaromatic polyamide composition (d) layer of composition (D1) or semiaromatic polyamide composition composition (D2), and stacking pipe is at least constituted by 4 layers.
In the stacking pipe of first method, it is necessary to include: (c) layer comprising EVOH (C) is combined comprising semiaromatic polyamide composition (d) layer of object (D1) or semiaromatic polyamide composition composition (D2), anti-chemical solution permeability, the especially anti-hydrocarbon that pipe is laminated are saturating The property crossed becomes good.
As preferred embodiment, (a) layer comprising fatty polyamide (A) is configured in the outermost layer of stacking pipe. By including (a) layer of fatty polyamide (A) in outermost layer configuration, it is excellent that chemical reagent resistance, flexibility can be obtained Stacking pipe.In addition, (c) layer comprising EVOH (C) is configured in (a) layer comprising fatty polyamide (A) and comprising semiaromatic Between (d) layer of polyamide composition (D1) or semiaromatic polyamide composition composition (D2).By including in innermost layer configuration (d) layer of semiaromatic polyamide composition composition (D1) or semiaromatic polyamide composition composition (D2), can obtain resistant to deterioration fuel Property excellent stacking pipe, further, it is possible to which the low molecular weight compositions such as monomer, oligomer are molten caused by inhibiting because of contact alcohol blended fuel Out.That is, preferably (a) layer is configured in outermost layer, (c) layer is configured in (a) layer and (d) the stacking pipe between layer.
Embodiment more preferably includes polyamides in at least side configuration adjacent with (c) layer comprising EVOH (C) 6 composition of amine (B1) and/or polyamide 6/66/12 composition (B2) (b) layer.By adjacent with (c) layer comprising EVOH (C) At least side configuration connect includes polyamide 6 composition (B1) and/or polyamide 6/66/12 composition (B2) (b) layer, can Excellent adhesiveness between layers are obtained, are combined with EVOH (C), semiaromatic polyamide composition composition (D1) or semiaromatic polyamide composition When object (D2) is coextruded, sufficient shape stability can be ensured within the scope of wide in range forming temperature.That is, more preferably In the stacking pipe of at least side configuration (b) layer adjacent with (c) layer.
In addition, in the stacking pipe of first method, if including the semiaromatic polyamide composition composition containing electroconductive stuffing (D1) or the conductive layer of semiaromatic polyamide composition composition (D2) is configured in the innermost layer that pipe is laminated, then anti-chemical solution penetrates Property, resistant to deterioration are fuel and excellent to the resistance to stripping property of monomer, oligomer, also, when being used as fuel distribution tube, can prevent because Fuel is caused to ignite in the spark that the interior internal friction of fuel recycled of piping or the friction of fuel and tube wall generate.This When, by making the layer comprising the semiaromatic polyamide composition without electric conductivity be configured in the outside relative to aforesaid conductive layer, Low-temperature impact resistance and electric conductivity can be taken into account, in addition, being economically also advantageous.
Electric conductivity refers to: for example, the feelings of the property fluid on fire continuously insulator of contact pressure resin etc in gasoline etc It is on fire although it is possible to electrostatic generation accumulation under condition, but the electrical characteristics for the degree that will not be accumulated with the electrostatic.As a result, can Enough prevent the explosion caused by electrostatic generated by fluids such as fuel in transport.
Electroconductive stuffing include in order to assign electric conductivity and all packing materials for adding to resin, can enumerate it is granular, Scale (flake) shape and bat wool etc..
As particulate filler, carbon black, graphite etc. can be enumerated.As flakey filler, aluminium scale, nickel squama can be enumerated Piece, nickel coated mica etc..In addition, can enumerate carbon fiber, carbon covering ceramic fibre, carbon whisker, carbon as bat wool and receive Metallic fibers such as mitron, aluminum fiber, copper fiber, brass fiber, stainless steel fibre etc..They can be used one kind or two or more. Among these, preferably carbon nanotube, carbon black.
Carbon nanotube is referred to as hollow carbon filament, which refers to: having interior hollow region and by regularly arranged The cylindrical shaft surrounding parenchyma of the carbon atom lateral area that continuous multilayer is formed in itself, each layer and hollow region in the fibril The upper substantially columned fibril in concentric arrangement.In turn, it is preferred that the regularly arranged carbon atom of above-mentioned lateral area For graphite-like, the diameter of above-mentioned hollow region is 2nm or more and 20nm or less.Fully dispersed property from resin, to gained From the perspective of resin molded body assigns satisfactory electrical conductivity, the outer diameter of carbon nanotube is preferably 3.5nm or more and 70nm or less, more Preferably 4nm or more and 60nm or less.The depth-width ratio (referring to the ratio between length/outer diameter) of carbon nanotube is preferably 5 or more, more preferably It is 100 or more, further preferably 500 or more.By meeting the depth-width ratio, conductive network easy to form, a small amount of addition is It can express excellent electric conductivity.
Carbon black includes that all carbon blacks commonly used in assigning electric conductivity can be enumerated as preferred carbon black by acetylene gas Section's qin that body is carried out acetylene black obtained from imperfect combustion, manufactured using crude oil as raw material and by furnace formula imperfect combustion Black equal furnace blacks, glossy black, naphthalene is black, thermal black, lampblack, channel black, roller black (roll black), disc black etc., but is not limited to it ?.Among these, more preferably acetylene black, furnace black.
In addition, carbon black is manufactured into the different various carbon dusts of the characteristics such as its partial size, surface area, DBP oil absorption, ash content. There is no limit, it is however preferred to have good chain structure and the big carbon blacks of gather density for the characteristic of the carbon black.From impact resistance Viewpoint is set out, and preferably not a large amount of compounding carbon blacks, from the viewpoint of obtaining excellent electrical conductivity with less amount, average grain diameter is preferred It is 500nm or less, more preferably 5nm or more and 100nm or less, further preferably 10nm or more and 70nm hereinafter, in addition, table Area (BET method) is preferably 10m2/ g or more, more preferably 30m2/ g or more, further preferably 50m2/ g or more, in turn, DBP (dibutyl phthalate) oil absorption is preferably 50ml/100g or more, more preferably 100ml/100g, is more preferably 150ml/100g or more.In addition, ash content is preferably 0.5 mass % or less, more preferably 0.3 mass % or less.Mentioned herein DBP oil absorption is the value measured according to method specified in ASTM D-2414.In addition, the volatile ingredient content of carbon black is preferably low In 1 mass %.
These electroconductive stuffings can be implemented to be surface-treated with the surface treating agent of titanate esters system, aluminium system, silane system etc..This Outside, in order to improve melting mixing workability, the filler through being granulated also can be used.
The content of electroconductive stuffing is different because of the type of the electroconductive stuffing used, can not lump together, from electric conductivity, From the perspective of the balance of mobility, mechanical strength etc., relative to semiaromatic polyamide composition (d1), semiaromatic polyamide composition (d2) 100 mass parts, it is often preferred that more than 3 mass parts and 30 below the mass.
In addition, about the electroconductive stuffing, from the viewpoint of obtaining sufficient antistatic property, melt extrudate Surface resistivity is preferably 108Ω/square or less, more preferably 106Ω/square or less.Wherein, above-mentioned electroconductive stuffing Addition be easy to cause the deterioration of intensity, mobility.Therefore, if the conductivity level of target can be obtained, it is expected that above-mentioned conduction The content of property filler is as few as possible.
In the stacking pipe of first method, the thickness of each layer is not particularly limited, can be according to the kind for the polymer for constituting each layer Class, total number of plies in stacking pipe, purposes etc. are adjusted, the thickness of each layer be contemplated that stacking pipe anti-chemical solution permeability, The characteristics such as low-temperature impact resistance, flexibility determine.In general, (a) layer, (b) layer, (c) layer, (d) layer thickness relative to The thickness of stacking pipe entirety is respectively preferably 3% or more and 90% or less.In view of low-temperature impact resistance and anti-chemical solution are saturating The balance for the property crossed, (c) layer, (d) layer thickness relative to stacking pipe entirety thickness respectively more preferably 5% or more and 50% with Under, further preferably 7% or more and 30% or less.
In addition, as long as total number of plies in the stacking pipe of first method has (a) layer comprising fatty polyamide (A), packet Containing polyamide 6 composition (B1) and/or polyamide 6/66/12 composition (B2) (b) layer, (c) layer comprising EVOH (C), with And (d) layer comprising semiaromatic polyamide composition composition (D1) or semiaromatic polyamide composition composition (D2) and at least 4 layers, just It is not particularly limited.In turn, the stacking pipe of first method is other than having (a) layer, (b) layer, (c) layer, this 4 layers of (d) layer The further stacking pipe for assigning function or obtaining economical advantages, it is possible to have 1 layer or 2 layers or more comprising other The layer of thermoplastic resin.The number of plies of the stacking pipe of first method is 4 layers or more, is judged from the mechanism of apparatus for producing tube, preferably 8 Layer is hereinafter, more preferably 5 layers or more and 7 layers or less.
The second method of stacking pipe includes (a) layer comprising fatty polyamide (A), comprising polyamide 6 composition (B1) And/or polyamide 6/66/12 composition (B2) (b) layer, comprising EVOH (C) (c) layer, comprising semiaromatic polyamide composition combine (d) layer and (e) layer comprising containing fluorine system polymer (E) of object (D1) or semiaromatic polyamide composition composition (D2), and it is described Stacking pipe is at least constituted by 5 layers.
In the stacking pipe of second method, it is necessary to include: (c) layer comprising EVOH (C) is combined comprising semiaromatic polyamide composition (d) layer of object (D1) or semiaromatic polyamide composition composition (D2), anti-chemical solution permeability, the especially anti-hydrocarbon that pipe is laminated are saturating The property crossed becomes good.In addition it is necessary to which containing (e) layer comprising containing fluorine system polymer (E), the anti-alcohol permeability that pipe is laminated becomes Well.It is excellent especially for the anti-permeability of the gasoline of the alcohol containing high concentration by the inclusion of (e) layer.
As preferred embodiment, (a) layer comprising fatty polyamide (A) is configured in the outermost layer of stacking pipe. By including (a) layer of fatty polyamide (A) in outermost layer configuration, it is excellent that chemical reagent resistance, flexibility can be obtained Stacking pipe.In addition, (c) layer comprising EVOH (C) and including semiaromatic polyamide composition composition (D1) or semi-aromatic polyamides (d) layer of amine composition (D2) is configured in (a) layer comprising fatty polyamide (A) and comprising containing fluorine system polymer (E) (e) between layer.By including (e) layer containing fluorine system polymer (E) in innermost layer configuration, it is fuel excellent that resistant to deterioration can be obtained Stacking pipe, further, it is possible to the low molecular weight compositions such as monomer, oligomer dissolution caused by inhibiting because of contact alcohol blended fuel.That is, Preferably (a) layer is configured in outermost layer, (c) layer and (d) layer is configured in (a) layer and (e) the stacking pipe between layer.
Embodiment more preferably includes polyamides in at least side configuration adjacent with (c) layer comprising EVOH (C) 6 composition of amine (B1) and/or polyamide 6/66/12 composition (B2) (b) layer.By adjacent with (c) layer comprising EVOH (C) At least side configuration connect includes polyamide 6 composition (B1) and/or polyamide 6/66/12 composition (B2) (b) layer, can Excellent adhesiveness between layers are obtained, are combined with EVOH (C), semiaromatic polyamide composition composition (D1) or semiaromatic polyamide composition When object (D2) and (E) containing fluorine system polymer are coextruded, can ensure within the scope of wide in range forming temperature adequately at Shape stability.That is, more preferably in the stacking pipe of at least side configuration (b) layer adjacent with (c) layer.
In addition, in the stacking pipe of second method, if leading comprising the fluorine-containing based polymer composition containing electroconductive stuffing Electric layer is configured in the innermost layer of stacking pipe, then the fuel and resistance to monomer of anti-chemical solution permeability, resistant to deterioration, oligomer dissolution Property it is excellent, also, when being used as fuel distribution tube, can prevent the internal friction of fuel because being recycled in piping or fuel with The friction of tube wall and the spark initiation fuel generated.At this point, by making comprising the layer containing fluorine system polymer without electric conductivity It is configured at the outside relative to aforesaid conductive layer, low-temperature impact resistance and electric conductivity can be taken into account, in addition, being economically also to have Benefit.It is in turn, mentioned herein to be also included within (E) containing fluorine system polymer in strand with functional group containing fluorine system polymer, Also refer to it is aftermentioned without functional group containing fluorine system polymer.
Electric conductivity and the details of electroconductive stuffing are identical as the stacking pipe of first method.
The content of electroconductive stuffing is different because of the type of the electroconductive stuffing used, can not lump together, from electric conductivity, From the perspective of the balance of mobility, mechanical strength etc., relative to 100 mass parts containing fluorine system polymer, it is often preferred that 3 mass Part or more and 30 below the mass.
In addition, about the electroconductive stuffing, from the viewpoint of obtaining sufficient antistatic property, melt extrudate Surface resistivity is preferably 108Ω/square or less, more preferably 106Ω/square or less.Wherein, above-mentioned electroconductive stuffing Addition be easy to incur the deterioration of intensity, mobility.Therefore, if the conductivity level of target can be obtained, it is expected that above-mentioned conduction The content of property filler is as few as possible.
In the stacking pipe of second method, the thickness of each layer is not particularly limited, can be according to the kind for the polymer for constituting each layer Class, total number of plies in stacking pipe, purposes etc. are adjusted, the thickness of each layer be contemplated that stacking pipe anti-chemical solution permeability, The characteristics such as low-temperature impact resistance, flexibility determine.In general, the thickness of (a) layer, (b) layer, (c) layer, (d) layer, (e) layer Thickness relative to stacking pipe entirety is respectively preferably 3% or more and 90% or less.In view of low-temperature impact resistance and anti-chemistry The balance of solution permeability, (c) layer, (d) layer, (e) layer thickness relative to stacking pipe entirety thickness respectively more preferably 5% Above and 50% or less, further preferably 7% or more and 30% or less.
In addition, as long as total number of plies in the stacking pipe of second method has (a) layer comprising fatty polyamide (A), packet Containing polyamide 6 composition (B1) and/or polyamide 6/66/12 composition (B2) (b) layer, (c) layer comprising EVOH (C), packet (d) layer of composition containing semiaromatic polyamide composition (D1) or semiaromatic polyamide composition composition (D2) and comprising poly- containing fluorine system (e) layer of object (E) and at least 5 layers are closed, are just not particularly limited.In turn, the stacking pipe of second method in addition to have (a) layer, (b) except this 5 layers of layer, (c) layer, (d) layer, (e) layer, in order to further assign function or obtain the stacking of economical advantages Pipe, it is possible to have 1 layer or 2 layers or more of the layer comprising other thermoplastic resins.The number of plies of the stacking pipe of second method is 5 layers More than, judge from the mechanism of apparatus for producing tube, preferably 8 layers or less, more preferably 6 layers or more and 7 layers or less.
As other thermoplastic resins in the stacking pipe of first method and second method, can enumerate in addition to aliphatic poly Except amide (A), semiaromatic polyamide composition (d1), semiaromatic polyamide composition (d2), poly-meta-xylylene adipamide (polyamide MXD6), poly- paraphenylene terephthalamide's m-xylene diamine (polyamide MXDT), it is poly- between phenyl-diformyl m-xylene diamine (polyamide MXDI), Poly- hexahydro paraphenylene terephthalamide m-xylene diamine (polyamide MXDT (H)), is gathered two formyl m-xylene diamine (polyamide MXDN) of poly- naphthalene Adipyl p dimethylamine (polyamide PXD6), poly- paraphenylene terephthalamide p dimethylamine (polyamide PXDT), it is poly- between phenyl-diformyl P dimethylamine (polyamide PXDI), poly- hexahydro paraphenylene terephthalamide p dimethylamine (polyamide PXDT (H)), two formyl pair of poly- naphthalene Benzene dimethylamine (polyamide PXDN), poly- mphenylen terephthalamide (PPIA), gathers at poly(p-phenylene terephthalamide) (PPTA) Paraphenylene terephthalamide's m-phenylene diamine (MPD) (PMTA), poly (PMIA), poly- (adipyl 2,6- naphthalene dimethylamine) are (poly- Amide 2,6-BAN6), poly- (paraphenylene terephthalamide's 2,6- naphthalene dimethylamine) (polyamide 2,6-BANT), poly- (phenyl-diformyl 2,6- naphthalene Dimethylamine) (polyamide 2,6-BANI), poly- (hexahydro paraphenylene terephthalamide's 2,6- naphthalene dimethylamine) (polyamide 2,6-BANT (H)), poly- (two formyl 2,6- naphthalene dimethylamine of naphthalene) (polyamide 2,6-BANN), poly- (adipyl 1,3- hexamethylene dimethylamine) (polyamide 1,3- It is BAC6), poly- that (suberoyl 1,3- hexamethylene dimethylamine (polyamide 1,3-BAC8), poly- (nonanedioyl 1,3- hexamethylene dimethylamine) are (poly- Amide 1,3-BAC9), poly- (decanedioyl 1,3- hexamethylene dimethylamine) (polyamide 1,3-BAD10), poly- (two acyl 1,3- ring of dodecane Hexane dimethylamine) (polyamide 1,3-BAD12), poly- (paraphenylene terephthalamide's 1,3- hexamethylene dimethylamine) (polyamide 1,3-BACT), Poly- (phenyl-diformyl 1,3- hexamethylene dimethylamine) (polyamide 1,3-BACI), poly- (hexahydro paraphenylene terephthalamide 1,3- hexamethylene two Methylamine) (polyamide 1,3-BACT (H)), poly- (two formyl 1,3- hexamethylene dimethylamine of naphthalene) (polyamide 1,3-BACN), poly- (1,4- Adipyl hexamethylene dimethylamine) (polyamide 1,4-BAC6), poly- (suberoyl 1,4- hexamethylene dimethylamine) (polyamide 1,4- BAC8), poly- (nonanedioyl 1,4- hexamethylene dimethylamine) (polyamide 1,4-BAC9), poly- (decanedioyl 1,4- hexamethylene dimethylamine) (polyamide 1,4-BAC10), poly- (two acyl 1,4- hexamethylene dimethylamine of dodecane) (polyamide 1,4-BAC12), poly- (terephthaldehyde Acyl 1,4- hexamethylene dimethylamine) (polyamide 1,4-BACT), poly- (phenyl-diformyl 1,4- hexamethylene dimethylamine) (polyamide 1,4- BACI), poly- (hexahydro paraphenylene terephthalamide's 1,4- hexamethylene dimethylamine) (polyamide 1,4-BACT (H)), poly- (two formyl 1,4- ring of naphthalene Hexane dimethylamine) (polyamide 1,4-BACN), poly- (adipyl 4,4 '-di-2-ethylhexylphosphine oxide cyclohexanediamine) (polyamide PACM6), poly- (suberoyl 4,4 '-di-2-ethylhexylphosphine oxide cyclohexanediamine) (polyamide PACM8), poly- (nonanedioyl 4,4 '-di-2-ethylhexylphosphine oxide cyclohexanediamine) are (poly- Amide PACM9), poly- (decanedioyl 4,4 '-di-2-ethylhexylphosphine oxide cyclohexanediamine) (polyamide PACM10), poly- (two acyl 4,4 ' of dodecane-sub- Methyl bicycle hexamethylene diamine) (polyamide PACM12), poly- (two 4,4 '-di-2-ethylhexylphosphine oxide of acyl cyclohexanediamine of the tetradecane) (polyamide PACM14), poly- (two 4,4 '-di-2-ethylhexylphosphine oxide of acyl cyclohexanediamine of hexadecane) (polyamide PACM16), poly- (two acyl 4,4 ' of octadecane- Di-2-ethylhexylphosphine oxide cyclohexanediamine) (polyamide PACM18), poly- (paraphenylene terephthalamide 4,4 '-di-2-ethylhexylphosphine oxide cyclohexanediamine) (polyamide PACMT), poly- (phenyl-diformyl 4,4 '-di-2-ethylhexylphosphine oxide cyclohexanediamine) (polyamide PACMI), it is poly- (hexahydro paraphenylene terephthalamide 4, 4 '-di-2-ethylhexylphosphine oxide cyclohexanediamine) (polyamide PACMT (H)), poly- (two 4,4 '-di-2-ethylhexylphosphine oxide of formyl cyclohexanediamine of naphthalene) (polyamide PACMN), poly- (adipyl 4,4 '-di-2-ethylhexylphosphine oxide (2- methyl cyclohexane diamines)) (polyamide MACM6), poly- (suberoyl 4,4 '-is sub- Methyl is bis- (2- methyl cyclohexane diamines)) (polyamide MACM8), poly- (nonanedioyl 4,4 '-di-2-ethylhexylphosphine oxide (2- methyl cyclohexane diamines)) (polyamide MACM9), poly- (decanedioyl 4,4 '-di-2-ethylhexylphosphine oxide (2- methyl cyclohexane diamines)) (polyamide MACM10), poly- (dodecane Two 4,4 '-di-2-ethylhexylphosphine oxides of acyl (2- methyl cyclohexane diamines)) (polyamide MACM12), poly- (two 4,4 '-di-2-ethylhexylphosphine oxide of acyl of the tetradecane (2- methyl cyclohexane diamines)) (polyamide MACM14), poly- (two 4,4 '-di-2-ethylhexylphosphine oxide of acyl of hexadecane (2- methyl cyclohexane diamines)) (polyamide MACM16), poly- (two 4,4 '-di-2-ethylhexylphosphine oxide of acyl of octadecane (2- methyl cyclohexane diamines)) (polyamide MACM18), gather (paraphenylene terephthalamide 4,4 '-di-2-ethylhexylphosphine oxide (2- methyl cyclohexane diamines)) (polyamide MACMT), poly- (phenyl-diformyl 4,4 '-methylene Base is bis- (2- methyl cyclohexane diamines)) (polyamide MACMI), poly- (hexahydro paraphenylene terephthalamide 4,4 '-di-2-ethylhexylphosphine oxide (2- methyl cyclohexane Diamines)) (polyamide MACMT (H)), poly- (two 4,4 '-di-2-ethylhexylphosphine oxide of formyl of naphthalene (2- methyl cyclohexane diamines)) (polyamide MACMN), poly- (the bicyclic hexamethylene diamine of adipyl 4,4 '-propylidene) (polyamide PACP6), poly- (suberoyl 4,4 '-propylidene is bicyclic Hexamethylene diamine) (polyamide PACP8), poly- (the bicyclic hexamethylene diamine of nonanedioyl 4,4 '-propylidene) (polyamide PACP9), it is poly- (decanedioyl 4, The bicyclic hexamethylene diamine of 4 '-propylidene) (polyamide PACP10), poly- (the two bicyclic hexamethylene diamine of 4,4 '-propylidene of acyl of dodecane) (polyamide PACP12), poly- (the two bicyclic hexamethylene diamine of 4,4 '-propylidene of acyl of the tetradecane) (polyamide PACP14), poly- (two acyl 4,4 ' of hexadecane- The bicyclic hexamethylene diamine of propylidene) (polyamide PACP16), poly- (the two bicyclic hexamethylene diamine of 4,4 '-propylidene of acyl of octadecane) (polyamide PACP18), poly- (the bicyclic hexamethylene diamine of paraphenylene terephthalamide 4,4 '-propylidene) (polyamide PACPT), poly- (phenyl-diformyl 4,4 '-is sub- The bicyclic hexamethylene diamine of propyl) (polyamide PACPI), poly- (the bicyclic hexamethylene diamine of hexahydro 4,4 '-propylidene of paraphenylene terephthalamide) (polyamide PACPT (H)), poly- (the two bicyclic hexamethylene diamine of 4,4 '-propylidene of formyl of naphthalene) (polyamide PACPN), poly hexamethylene adipamide isophorone diamine (polyamide IPD6), poly- suberoyl isophorone diamine (polyamide IPD8), poly- nonanedioyl isophorone diamine (polyamide IPD9), poly- decanedioyl isophorone diamine (polyamide IPD10), two acyl isophorone diamine (polyamide of poly- dodecane IPD12), poly- paraphenylene terephthalamide's isophorone diamine (polyamide IPDT), it is poly- between phenyl-diformyl isophorone diamine (polyamide IPDI), poly- hexahydro paraphenylene terephthalamide isophorone diamine (polyamide IPDT (H)), two formyl isophorone diamine (polyamides of poly- naphthalene Amine IPDN), poly- paraphenylene terephthalamide's butanediamine (polyamide 4T), it is poly- between phenyl-diformyl butanediamine (polyamide 4I), poly- hexahydro to benzene Two formyl butanediamine (polyamide 4T (H)), two formyl butanediamine (polyamide 4N) of poly- naphthalene, poly- paraphenylene terephthalamide's pentanediamine (polyamides Amine 5T), it is poly- between phenyl-diformyl pentanediamine (polyamide 5I), poly- hexahydro paraphenylene terephthalamide pentanediamine (polyamide 5T (H)), poly- naphthalene two Formyl pentanediamine (polyamide 5N), poly- hexamethylene terephthalamide (polyamide 6 T), poly-6I hexamethylene isoterephalamide (polyamide 6I), poly- hexahydro hexamethylene terephthalamide (polyamide 6 T (H)), two formyl hexamethylene diamine (polyamide 6 N) of poly- naphthalene, poly- (to benzene two Formyl 2 methyl pentamethylenediamine) (polyamide M5T), poly- (phenyl-diformyl 2 methyl pentamethylenediamine) (polyamide M5I), poly- (hexahydro pair Phenyl-diformyl 2 methyl pentamethylenediamine) (polyamide M5T (H)), poly- (two formyl 2 methyl pentamethylenediamine (polyamide M5N) of naphthalene, poly- hexahydro Paraphenylene terephthalamide's nonamethylene diamine (polyamide 9T (H)), gathers poly- (hexahydro paraphenylene terephthalamide's 2- methyl octamethylenediamine) (polyamide M8T (H)) Between phenyl-diformyl trimethylhexane diamine (polyamide TMHI), poly- hexahydro paraphenylene terephthalamide trimethylhexane diamine (polyamide TMHT (H)) phenyl-diformyl decamethylene diamine (polyamide 10I) between, gathering, poly- hexahydro paraphenylene terephthalamide decamethylene diamine (polyamide 10T (H)), it is poly- between Phenyl-diformyl hendecane diamines (polyamide 11I), poly- hexahydro paraphenylene terephthalamide hendecane diamines (polyamide 11T (H)), poly- isophthalic Two formyl dodecamethylene diamines (polyamide 12I), use these at poly- hexahydro paraphenylene terephthalamide dodecamethylene diamine (polyamide 12T (H)) Copolymer obtained from a variety of in the starting monomer of the starting monomer of polyamide and/or aforementioned fatty polyamide (A) etc. is poly- Amide system resin.
In addition, polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF), polytetrafluoroethylene (PTFE) (PTFE), poly- trifluoro can be enumerated Vinyl chloride (PCTFE), tetrafluoroethylene/perfluoro (alkyl vinyl ether) copolymer (PFA), tetrafluoroethylene/hexafluoropropylene copolymer (FEP), tetrafluoroethylene/perfluoro (alkyl vinyl ether)/hexafluoropropylene copolymer, Tefzel (ETFE), second Alkene/tetrafluoroethylene/hexafluoropropylene copolymer (EFEP), vinylidene fluoride/tetrafluoroethylene copolymer, vinylidene fluoride/hexafluoro third Alkene copolymer, vinylidene fluoride/perfluor (alkyl vinyl ether) copolymer, tetrafluoroethylene/hexafluoropropylene/vinylidene fluoride copolymerization Object (THV), vinylidene fluoride/perfluor (alkyl vinyl ether)/TFE copolymer, tetrafluoroethylene/hexafluoropropylene/inclined difluoro Ethylene/perfluor (alkyl vinyl ether) copolymer, ethylene/chlorotrifluoroethylene (ECTFE), chlorotrifluoroethylene/tetrafluoro second Alkene copolymer, vinylidene fluoride/chlorotrifluoroethylene, chlorotrifluoroethylene/perfluor (alkyl vinyl ether) copolymer, trifluoro Vinyl chloride/hexafluoropropylene copolymer, chlorotrifluoroethylene/tetrafluoroethylene/hexafluoropropylene copolymer, chlorotrifluoroethylene/tetrafluoroethene/ Vinylidene fluoride copolymer, chlorotrifluoroethylene/perfluor (alkyl vinyl ether)/TFE copolymer (CPT), trifluoro chloroethene Alkene/perfluor (alkyl vinyl ether)/hexafluoropropylene copolymer, chlorotrifluoroethylene/tetrafluoroethylene/hexafluoropropylene/perfluor (alkyl second Alkene ether) copolymer, chlorotrifluoroethylene/tetrafluoroethene/vinylidene fluoride/perfluor (alkyl vinyl ether) copolymer, trifluoro chlorine Ethylene/tetrafluoroethylene/vinylidene fluoride/hexafluoropropylene copolymer, chlorotrifluoroethylene/tetrafluoroethene/vinylidene fluoride/perfluor (alkyl vinyl ether)/hexafluoropropylene copolymer etc., which is free of, contains fluorine system polymer with reactive functional group to amino.
Stacking pipe has (e) layer comprising containing fluorine system polymer (E), and contain fluorine system polymer (E) includes aforementioned right When amino has reactive functional group, configured by the layer that will include the fluorine system polymer without functional group relative to (e) The inside of layer, can take into account low-temperature impact resistance, anti-chemical solution permeability and environmental stress resistance cracking, in addition, in economy On be also advantageous.It should be noted that having imported in strand has the poly- containing fluorine system of reactive functional group to amino Object (E) is closed to be only contained in (e) layer.
In turn, high density polyethylene (HDPE) (HDPE), medium density polyethylene (MDPE), low density polyethylene (LDPE) can be enumerated (LDPE), straight-chain low density polyethylene (LDPE) (LLDPE), ultra-high molecular weight polyethylene (UHMWPE), polypropylene (PP), polybutene (PB), polymethylpentene (TPX), ethylene/propene copolymer (EPR), ethylene/butylene copolymers (EBR), ethylene/acetic acid ethylene Ester copolymer (EVA), ethylene/acrylic acid copolymer (EAA), ethylene/methacrylic acid (EMAA), ethylene/acrylic acid Methyl terpolymer (EMA), ethylene/methacrylic acid methyl terpolymer (EMMA), ethylene/ethyl acrylate copolymer (EEA) etc. Polyolefin-based resins；Polystyrene (PS), syndiotactic polystyrene (SPS), methyl methacrylate/styrol copolymer (MS), methyl methacrylate/styrene/butadiene copolymers (MBS), styrene/butadiene copolymers (SBR), styrene/ Isoprene copolymer (SIR), styrene/isoprene/butadiene copolymer (SIBR), styrene/butadiene/styrene are total Polymers (SBS), styrene/isoprene/styrene copolymer (SIS), styrene/ethylene/butylene/styrene copolymer (SEBS), the polystyrene resins such as styrene/ethylene/propylene/styrene copolymer (SEPS)；Acrylic acid, methacrylic acid, Maleic acid, fumaric acid, itaconic acid, crotonic acid, mesaconic acid, citraconic acid, glutaconate, cis- -4- cyclohexene -1,2- dicarboxylic acids, Bridge-is bicyclic-and [2.2.1] -5- heptene -2,3- dicarboxylic acids etc. contains carboxyl and its metal salt (Na, Zn, K, Ca, Mg), maleic acid Acid anhydride, itaconic anhydride, citraconic anhydride, bridge-be bicyclic-anhydride groups, the acrylic acid such as [2.2.1] -5- heptene -2,3- dicarboxylic anhydride shrink it is sweet Grease, glycidyl methacrylate, glycidyl ethacrylate, glycidyl itoconate, citraconic acid shrink sweet Said polyolefins system resin, the polystyrene resin, polybutylene terephthalate (PBT) of the functional groups such as the epoxy groups such as grease (PBT), polyethylene terephthalate (PET), polyethylene glycol isophthalate (PEI), poly- (terephthalate Ester/ethylene isophthalate) copolymer (PET/PEI), polypropylene terephthalate (PTT), poly terephthalic acid Cyclohexanedimethanoester ester (PCT), polyethylene naphthalate (PEN), polybutylene naphthalate (PBN), polyarylate (PAR), the polyester based resins such as liquid crystal polyester (LCP), polylactic acid (PLA), polyglycols sour (PGA)；Polyacetals (POM), polyphenylene oxide (PPO) the polyether systems resin such as；The polysulfones system resins such as polysulfones (PSU), polyether sulfone (PESU), polyphenylsulfone (PPSU)；Polyphenylene sulfide (PPS), the polythiaethers system such as poly thioether sulfone (PTES) resin；Polyketone (PK), polyether-ketone (PEK), polyether-ether-ketone (PEEK), polyether-ketone Ketone (PEKK), polyethers ether ether ketone (PEEEK), polyether ether ketone ketone (PEEKK), polyether ketone ketone ketone (PEKKK), polyetherketoneetherketoneketone (PEKEKK) the polyketone system resin such as；Polyacrylonitrile (PAN), polymethacrylonitrile, acrylonitrile/styrol copolymer (AS), methyl Acrylonitrile/styrol copolymer, acrylonitrile/butadiene/styrene copolymer (ABS), acrylonitrile/butadiene copolymer (NBR) Equal polynitriles system resin；The polymethacrylates systems such as polymethyl methacrylate (PMMA), polyethyl methacrylate (PEMA) Resin；The polyvinyl esters system such as polyvinyl acetate (PVAc) resin；Polyvinylidene chloride (PVDC), polyvinyl chloride (PVC), chloroethene The polyvinyl chloride resins such as alkene/vinylidene chloride copolymer, vinylidene chloride/methyl acrylate copolymer；Cellulose acetate, fourth The cellulose-based resins such as acid cellulose；The polycarbonate-based resins such as polycarbonate (PC)；Thermoplastic polyimide (TPI), polyethers The polyimides system resins such as acid imide, polyesterimide, polyamidoimide (PAI), imide；Thermoplastic poly ammonia Ester system resin, polyamide elastomer, polyurethane elastomer, polyester elastomer etc..
In addition, in the stacking pipe of first method, from the viewpoint of the melt stability of EVOH (C), in above-mentioned illustration Thermoplastic resin among, it is preferable to use fusing point is 290 DEG C of polyester based resins below, polyamide resin, polythiaether system tree Rouge, polyolefin-based resins and fluorine system polymer.
In addition, in the stacking pipe of second method, from the viewpoint of the melt stability of EVOH (C), in above-mentioned illustration Thermoplastic resin among, it is preferable to use fusing point is 290 DEG C of polyester based resins below, polyamide resin, polythiaether system tree Rouge, polyolefin-based resins and the fluorine system polymer without functional group.
In addition it is also possible to any substrate other than thermoplastic resin is laminated, such as stacking paper, metal based material, not It stretches, uniaxial or biaxial stretching plastic film or piece, fabric, non-woven fabrics, metal wool, timber etc..As metal based material, can arrange Enumerate the metals such as aluminium, iron, copper, nickel, gold, silver, titanium, molybdenum, magnesium, manganese, lead, tin, chromium, beryllium, tungsten, cobalt, metallic compound and by this Alloy types such as copper alloys, the nickel alloys such as steel alloys, aluminium alloy, brass, the bronze such as the stainless steel of two or more formation in a little etc..
As stacking pipe manufacturing method, the following methods can be enumerated: being squeezed out using corresponding with layer number or material quantity Machine carries out melting extrusion, in mould inside or the method for external stacking simultaneously (coextrusion forming process)；Alternatively, temporarily previously fabricated Mono-layer tube or the stacking pipe manufactured using the above method, successively use bonding agent as needed on the outside, and resin is made to carry out one Body and the method (coating method) being laminated.Stacking pipe is preferably manufactured by coextrusion forming process, the coextrusion forming process Refer to: a variety of materials are coextruded in the molten state, makes the two thermal welding (melting adhered) in one step Manufacture the pipe of stepped construction.That is, the manufacturing method of stacking pipe preferably includes to carry out coextrusion forming.
In addition, implementing heating bending machining in the case that gained stacking pipe is complicated shape after forming and forming being made In the case where product, for the residual strain of Material removal product, aforementioned pipe can also be constituted to be lower than after forming above-mentioned stacking pipe Resin fusing point among the temperature of minimum fusing point carry out 0.01 hour or more and heat treatment below in 10 hours, to obtain mesh Mark formed products.
It can have wave regions in stacking pipe.Wave regions refer to: being formed as waveform shape, snake abdomen shape, accordion The region of shape or corrugated shape etc..Not only can endlong have wave regions throughout stacking pipe, can also on the way fit When region locally has wave regions.After wave regions can be by being configured to the pipe of straight tube-like first, then carry out mold at Specific waveform shape etc. is made to be readily formed in shape.By with the wave regions, so that there is impact absorbency, Installation becomes easy.In turn, such as by the necessary component such as additional connector or bending machining is carried out, L can be made Word, shape of U-shaped etc..
For all or part of periphery for the stacking pipe being shaped so as to, it is contemplated that slungshot, the mill with other components Consumption and fire resistance, can be arranged by natural rubber (NR), butadiene rubber (BR), isoprene rubber (IR), butyl rubber (IIR), chloroprene rubber (CR), carboxylated butadiene rubber (XBR), carboxylated chloroprene rubber (XCR), epoxy chloropropionate Alkane rubber (ECO), acrylonitrile butadiene rubber (NBR), hydrogenated acrylonitrile butadiene rubber (HNBR), carboxylated acrylonitrile nitrile fourth two Alkene rubber (XNBR), the mixture of NBR and polyvinyl chloride, nitrile isoprene rubber (NIR), chlorinated polyethylene rubber (CM), chlorine sulfone polyethylene rubber (CSM), ethylene propylene rubber (EPR), ethylene propylene diene rubber (EPDM), vinyl acetate Vinyl acetate rubber (EVM), the mixture rubber of NBR and EPDM, acrylic rubber (ACM), ethylene acrylic rubber (AEM), acrylate butadiene rubber (ABR), styrene butadiene ribber (SBR), carboxylated styrene butadiene rubber (XSBR), SIR styrene isoprene rubber (SIR), styrene isoprene butadiene rubber (SIBR), urethane rubber, Silicone rubber (MQ, VMQ), fluorubber (FKM, FFKM), flurosilicone rubber (FVMQ), vinyl chloride, olefin-based, ester system, amino The solids of compositions such as the thermoplastic elastomer (TPE)s such as formic acid esters system, amide system or spongiform guard block (guard member).Guard block Spongiform porous body can also be made by known gimmick.By the way that porous body is made, it is capable of forming light weight and insulation The excellent protection portion of property.Additionally it is possible to reduce material cost.Alternatively, glass fibre etc. can also be added to improve its intensity. The shape of guard block is not particularly limited, and usually has the block-wise portion of the recess portion for accommodating cartridge or stacking pipe Part.In the case where cartridge, stacking pipe can be subsequently inserted into the cartridge of pre-production, or on stacking pipe Covering squeezes out cartridge and makes the two is closely sealed.In order to be bonded the two, pass through the inner surface in guard block Or aforementioned concave surface coating adhesive as needed, stacking pipe is inserted into or inlayed thereto, the two is closely sealed, to form stacking pipe Structural body integrated with guard block.In addition it is also possible to be enhanced with metal etc..
Outer diameter about stacking pipe, it is contemplated that the flow of chemical solution (such as the fuel such as alcohol blended fuel) etc., wall thickness are set The thickness that not will increase the permeability of chemical solution and be able to maintain that the breakdown pressure of common tube is counted into, and is designed to The thickness of the flexibility of the good degree of vibration resistance when enough maintaining the installation exercise easiness of pipe and using, but do not limit It is fixed.Outer diameter is preferably 4mm or more and 300mm hereinafter, internal diameter is preferably 3mm or more and 250mm hereinafter, wall thickness is preferably 0.5mm Above and 25mm or less.
The stacking pipe of present embodiment can be used for machinery such as automobile component, internal combustion engine purposes, electric power tool shell classes Industrial materials, industry goods, materials and equipments, electrical and electronic parts, medical treatment, food, work-at-home articles, building materials headed by component are related The various uses such as component, furniture component.
In addition, the anti-chemical solution permeability of stacking pipe is excellent, therefore it is suitable as chemical solution delivery tube.As chemistry Solution, such as the aromatic hydrocarbon solvents such as benzene,toluene,xylene can be enumerated；Methanol, ethyl alcohol, propyl alcohol, butanol, amylalcohol, second two The alcohol such as alcohol, propylene glycol, diethylene glycol, phenol, cresols, polyethylene glycol, polypropylene glycol；Phenolic solvent；Dimethyl ether, dipropyl ether, first The ether solvents such as the tertiary butyl ether of base, the tertiary butyl ether of ethyl-, dioxanes, tetrahydrofuran；Chloroform, methylene chloride, trichloro ethylene, dichloroethylene, The halogen solvents such as perchloroethylene, monochloroethane, dichloroethanes, tetrachloroethanes, perchloroethane, chlorobenzene；Ethyl ketone, methyl ethyl ketone, diethyl The ketone solvents such as ketone, acetophenone；Oxygenated gasoline, amine-containing gasoline, acid is blended in gasoline, kerosene, diesel oil, alcohol blended fuel, ethyl tert-butyl ether Property gasoline, castor oil-base brake fluid, glycol ethers system brake fluid, borate system brake fluid, polar region brake fluid, silicone oil system braking Liquid, mineral oil system brake fluid, power steering gear oil, sulfide hydrogen oil, air window washing liquid, engine coolant, urea liquid, Medicament, ink, coating etc..Stacking pipe be suitable as transporting the pipe of above-mentioned chemical solution, specifically, can enumerate feed pipe, The cartridges such as return pipe, vaporizer tube, fuel feed pipe, ORVR pipe, storage tube, ventilation duct；Oil pipe, petroleum excavate pipe, braking Pipe, air window washing liquid pipe, engine coolant (LLC) pipe, holding vessel pipe, urea liquid delivery tube, cooling water, refrigerant etc. With cooling tube, air-conditioning refrigerant pipe, heater tube, road heater pipe, floor heating pipe, infrastructure plan pipe, fire extinguisher With pipe used for fire-extinguishing equipment, medical cooler material pipe, ink, coating diffusion tube, other chemical solution liquid pipes.It is particularly suitable for making For cartridge.That is, the present invention includes the purposes as the cartridge of aforementioned stacking pipe.
Embodiment
Embodiment described below and comparative example illustrate the present invention, but the present invention is not limited thereto.It needs to illustrate It is material used in the analysis and physical property measurement method and embodiment and the comparative example that show in embodiment and comparative example.
The characteristic of polyamide resin is measured using following methods.
[relative viscosity]
According to JIS K-6920, in 96% sulfuric acid, under conditions of polymer concentration is 1%, temperature is 25 DEG C into Row measurement.
[terminal amino group concentration]
The polyamide sample that specific quantity is put into the conical flask with plug, adds previously prepared solvent phenol/methanol After (volume ratio 9/1) 40mL, it is stirred dissolution with magnetic stirring apparatus, indicator uses thymol blue, with the hydrochloric acid of 0.05N It is titrated, so as to find out terminal amino group concentration.
[end carboxy concentration]
The polyamide sample that specific quantity is put into three mouthfuls of eggplant type flasks soaks under stream of nitrogen gas after adding benzylalcohol 40mL Stain is in the oil bath for being set as 180 DEG C.It is stirred dissolution by the stirring motor that top is installed, indicator uses phenolphthalein, uses The sodium hydroxide solution of 0.05N is titrated, and end carboxy concentration is found out.
In addition, the characteristic containing fluorine system polymer is measured using following methods.
[composition containing fluorine system polymer]
It is measured by melting NMR analysis, fluorine content analysis, infrared absorption spectrum.
[containing the terminal carbonate radix amount in fluorine system polymer]
About containing the terminal carbonate radix amount in fluorine system polymer, by infrared absorption spectrum analysis, carbonate group (- OC (=O) O-) the peak that is belonged to of carbonyl appear in 1817cm-1Absorbing wavelength at, the absorbance of absorption peak is measured, under Formula calculate containing in fluorine system polymer relative to main chain carbon number 106A carbonate group number.
[containing in fluorine system polymer relative to main chain carbon number 106A carbonate group number]=500AW/ ε df
A: the absorbance at the peak of carbonate group (- OC (=O) O-)
ε: the molar absorptivity coefficient [cm of carbonate group (- OC (=O) O-)-1·mol-1].According to model compound, if For ε=170.
W: average molecular weight is formed by what monomer composition calculated
D: the density [g/cm of film3]
F: the thickness [mm] of film
In addition, each physical property of stacking pipe is measured using following methods.
[low-temperature impact resistance]
According to method described in VW TL 52,435 6.5, implement impact test at -40 DEG C.
[resistant to deterioration is fuel]
According to method described in SAE J-2260 7.8, implement the test of resistant to deterioration fuel.For the pipe after test, according to Method described in SAE J-2260 7.5, implements impact test at -40 DEG C, relative to test radical 10, in fracture radical When being 0, judge that its resistant to deterioration is fuel excellent.
[anti-chemical solution (alcohol blended fuel (CE10)) permeability]
One end sealing that the pipe of 200mm will be cut into, internally puts into FuelC (isooctane/toluene=50/50 volume Than) and the alcohol blended fuel (CE10) that is mixed to get with 90/10 volume ratio of ethyl alcohol, remaining one end also seals.Thereafter, it measures whole The quality of body then puts into developmental tube into 60 DEG C of baking oven, daily quality measurement variation.Pass through average one day quality Variation calculates alcohol blended fuel transit dose (CE10) (g/m divided by pipe internal surface product2·day)。
[anti-chemical solution (alcohol blended fuel (CE85)) permeability]
One end sealing that the pipe of 200mm will be cut into, internally puts into FuelC (isooctane/toluene=50/50 volume Than) and the alcohol blended fuel (CE85) that is mixed to get with 15/85 volume ratio of ethyl alcohol, remaining one end also seals.Thereafter, it measures whole The quality of body then puts into developmental tube to 60 DEG C of baking oven, daily quality measurement variation.Become by average one day quality It eliminates and is accumulated with pipe internal surface to calculate alcohol blended fuel transit dose (CE85) (g/m2·day)。
[adhesiveness between layers]
By the pipe for cutting into 200mm further along half is slit longitudinally into, testing piece is made.Use universal testing machine (ORIENTEC corporation, TENSILON UTM III-200) implements 180 ° of disbonded tests with the tensile speed of 50mm/min.By The maximum of S-S curve reads peel strength, evaluates adhesiveness between layers.
[adhesiveness between layers after heat treatment]
The pipe for cutting into 200mm is put into 160 DEG C of baking oven, is handled 12 minutes.It is taken according to preceding method evaluation The adhesiveness between layers of pipe out.When peel strength after heat treatment is 20N/cm or more, it is judged as the durability of adhesiveness between layers It is excellent.
[resistance to monomer, oligomer stripping property]
The close bolt in one end that the pipe of 0.5m will be cut into internally is put into FuelC (isooctane/toluene=50/50 volume Than) and the alcohol blended fuel (CE10) that is mixed to get with 90/10 volume ratio of ethyl alcohol, remaining one end is also sealed.Thereafter, it will try It tests pipe to put into 60 DEG C of baking oven, handle 48 hours.After treatment, by the alcohol blended fuel in the pipe of taking-up with 0 DEG C of cooling It after 24 hours, is filtered with the filter (material: polyether sulfone) that aperture is 0.45 μm, the quality of measurement trapping object.By trapping object Quality divided by processing number of days and pipe internal surface area, to calculate monomer, oligomer the amount of dissolution (g/m2·day).In addition, After treatment, from also being carried out visually to the tone for the alcohol blended fuel extracted out out of pipe.
[material used in embodiment and comparative example]
The manufacture of 12 composition of polyamide (A-1)
It is pre- in polyamide 12 (a-1) (Ube Industries, Ltd's system, UBESTA 3030UX1, relative viscosity 2.21) First maleic anhydride modified ethylene/propene copolymer (JSR Corp. system, JSR T7761P of the mixing as modified impact material； According to ISO 178 measure bending elastic modulus: 5MPa), as the bis- [3- (3- tert-butyl -5- first of triethylene glycol of antioxidant Base -4- hydroxy phenyl) propionic ester] (BASF JAPAN corporation, IRGANOX245) and as the three of phosphorus system processing stabilizers (2,4- di-tert-butyl-phenyl) phosphite ester (BASF JAPAN corporation, IRGAFOS168), and supply mixed to twin-screw melting Mill (Corporation Japan Steel Works' system, model: TEX44), in addition, from the machine barrel midway of the twin-screw melting mixing machine, benefit Use constant displacement pump injection as the benzene sulfonic acid butyramide of plasticizer, it, will with 260 DEG C of progress melting mixings from 180 DEG C of barrel temperature It after molten resin is extruded into strand form, is conducted into sink, cool down, cut, be dried in vacuo, obtain relative to polyamides Total 100 mass parts of 12 85 mass % of amine, 10 mass % of modified impact material, 5 mass % of plasticizer, include antioxidant The pellet of 12 composition of polyamide of 0.8 mass parts, 0.2 mass parts of phosphorus system processing stabilizers is (hereinafter, combine the polyamide 12 Object is known as (A-1)).
The manufacture of 12 composition of polyamide (A-2)
In the manufacture of 12 composition of polyamide (A-1), plasticizer is not used, changes the additive amount of modified impact material, In addition to this, it using method identical with the manufacture of 12 composition of polyamide (A-1), obtains relative to 12 85 matter of polyamide Total 100 mass parts for measuring %, 15 mass % of modified impact material, include 0.8 mass parts of antioxidant, phosphorus system processing stabilizers The pellet (hereinafter, 12 composition of polyamide is known as (A-2)) of 12 composition of polyamide of 0.2 mass parts.
The manufacture of 12 composition of Electrical Conductive Polyamide (A-3)
In the manufacture of 12 composition of polyamide (A-1), polyamide 12 (a-1) is changed to (the space portion polyamide 12 (a-2) Emerging production Co. Ltd. system, UBESTA 3020U, relative viscosity 1.86), use carbon black (Cabot Corp. system, Balkan XD- 72) be used as electroconductive stuffing, do not use plasticizer, barrel temperature is changed to 270 DEG C from 260 DEG C, in addition to this, using with it is poly- The identical method of manufacture of 12 composition of amide (A-1) is obtained relative to 12 60 mass % of polyamide, modified impact material 20 Total 100 mass parts of quality %, 20 mass % of electroconductive stuffing, include 0.8 mass parts of antioxidant, phosphorus system processing stabilizers The pellet of 12 composition of Electrical Conductive Polyamide of 0.2 mass parts is (hereinafter, be known as (A- for 12 composition of Electrical Conductive Polyamide 3))。
The manufacture of polyamide 610 (a-3) or (b-3)
To internal volume be put into 70 liters of the compression resistance reaction vessel with blender 1,6- hexamethylene diamine and decanedioic acid etc. 50 mass % aqueous solution 17.6kg, 1, the 6- hexamethylene diamine 40.0g of molar salt are heated to after carrying out nitrogen displacement in polymerization tank It 220 DEG C, is stirred at such a temperature to reaching uniform state in reaction system.Then, the temperature in polymerization tank is made to be warming up to 270 DEG C, pressure in slot is adjusted to 1.7MPa on one side, is polymerize under stirring in 2 hours on one side.Thereafter, about 2 hours are expended to bleed off pressure It then is decompressed to 53kPa to normal pressure, carries out polymerization in 4 hours under reduced pressure.Then, nitrogen is directed into autoclave, it is extensive It answers to normal pressure, is taken out, cut to obtain pellet in the form of strand from the lower nozzle of reaction vessel.By the pellet into Row is dried under reduced pressure, and obtains that relative viscosity is 3.05, terminal amino group concentration is 50 μ eq/g, end carboxy concentration is the poly- of 14 μ eq/g Amide 610 (hereinafter, the polyamide 610 is known as (a-3) or (b-3)).
The manufacture of polyamide 610 composition (A-4)
In the manufacture of 12 composition of polyamide (A-1), polyamide 12 (a-1) is changed to polyamide 610 (a-3), it will Barrel temperature is changed to 270 DEG C from 260 DEG C, in addition to this, utilizes side identical with the manufacture of 12 composition of polyamide (A-1) Method, obtain relative to 80 mass % of polyamide 610,10 mass % of modified impact material, 10 mass % of plasticizer total 100 Mass parts, the pellet of the polyamide 610 composition comprising 0.8 mass parts of antioxidant, 0.2 mass parts of phosphorus system processing stabilizers (hereinafter, the polyamide 610 composition is known as (A-4)).
The manufacture of polyamide 612 (a-4) or (b-4)
It is in the manufacture of polyamide 610 (a-3), 50 mass % of 1,6- hexamethylene diamine and the equimolar salt of decanedioic acid are water-soluble Liquid 17.6kg is changed to 50 mass % aqueous solution 19.2kg of the equimolar salt of 1,6- hexamethylene diamine and dodecanedioic acid, by 1,6- oneself The additive amount of diamines is changed to 43.5g from 40.0g, in addition to this, using method identical with the manufacture of polyamide 610 (a-3), Obtain relative viscosity be 2.78, terminal amino group concentration is 51 μ eq/g, polyamide 612 that end carboxy concentration is 14 μ eq/g (with Under, which is known as (a-4) or (b-4)).
The manufacture of polyamide 612 composition (A-5)
In the manufacture of 12 composition of polyamide (A-1), polyamide 12 (a-1) is changed to polyamide 612 (a-4), it will Barrel temperature is changed to 270 DEG C from 260 DEG C, in addition to this, utilizes side identical with the manufacture of 12 composition of polyamide (A-1) Method, obtain relative to 80 mass % of polyamide 612,10 mass % of modified impact material, 10 mass % of plasticizer total 100 Mass parts, the pellet of the polyamide 612 composition comprising 0.8 mass parts of antioxidant, 0.2 mass parts of phosphorus system processing stabilizers (hereinafter, the polyamide 612 composition is known as (A-5)).
The manufacture of polyamide 6 composition (B1-1)
In the manufacture of 12 composition of polyamide (A-1), polyamide 12 (a-1) is changed to (the space portion polyamide 6 (b-1) Emerging production Co. Ltd. system, UBE NYLON 1030B, relative viscosity 3.89), barrel temperature is changed to 270 DEG C from 260 DEG C, is removed Except this, using method identical with the manufacture of 12 composition of polyamide (A-1), obtain relative to 80 mass % of polyamide 6, Total 100 mass parts of 10 mass % of modified impact material, 10 mass % of plasticizer, include 0.8 mass parts of antioxidant, phosphorus system The pellet (hereinafter, the polyamide 6 composition is known as (B1-1)) of the polyamide 6 composition of 0.2 mass parts of processing stabilizers.
The manufacture of polyamide 6/66/12 (b-2)
To internal volume be in 70 liters of the compression resistance reaction vessel with blender investment caprolactam 16.2kg, 1,6- oneself two 50 mass % aqueous solution 5.0kg and 12 amino dodecanoic acid 2.5kg of the equimolar salt of amine and decanedioic acid, are heated to 100 DEG C, it is stirred at such a temperature to reaching uniform state in reaction system.Then, temperature is further made to be warming up to 260 DEG C, It is stirred 1 hour under the pressure of 2.5MPa.Thereafter, bleed off pressure on one side and be vaporized moisture from reaction vessel, on one side under normal pressure with 260 DEG C carry out 2 hours polymerization reactions, and then 7 hours polymerization reactions are carried out under 260 DEG C, the decompression of 53kPa.Reaction knot Shu Hou is directed into sink at the reactant of strand form for taking out from the lower nozzle of reaction vessel, is cooled down and cut, thus Obtain pellet.In the hot water by pellet dipping, it after extracting and removing unreacted monomer, is dried under reduced pressure, to obtain phase Polyamide 6/66/12 (the hexanoyl amine unit/hexamethyleneadipamide unit/dodecanoyl amine unit=78/ for being 4.01 to viscosity 11/11 mass %) (hereinafter, polyamide 6/66/12 is known as (b-2)).
The manufacture of polyamide 6/66/12 composition (B2-1)
In the manufacture of 12 composition of polyamide (A-1), polyamide 12 (a-1) is changed to polyamide 6/66/12 (b-2) It in addition to this using method identical with the manufacture of 12 composition of polyamide (A-1), is obtained opposite with polyamide 610 (b-3) In polyamide 6/66,/12 50 mass %, 30 mass % of polyamide 610,15 mass % of modified impact material, 5 matter of plasticizer Total 100 mass parts for measuring %, comprising 0.8 mass parts of antioxidant, 0.2 mass parts of phosphorus system processing stabilizers polyamide 6/ The pellet (hereinafter, the polyamide 6/66/12 composition is known as (B2-1)) of 66/12 composition.
The manufacture of polyamide 6/66/12 composition (B2-2)
In the manufacture of polyamide 6/66/12 composition (B2-1), polyamide 610 (b-3) is changed to polyamide 612 (b-4), it in addition to this, using method identical with polyamide 6/manufacture of 66/12 composition (B2-1), obtains relative to polyamides The conjunction of 6,/66,/12 50 mass % of amine, 30 mass % of polyamide 612,15 mass % of modified impact material, 5 mass % of plasticizer 100 mass parts are counted, polyamide 6/66/12 combination comprising 0.8 mass parts of antioxidant, 0.2 mass parts of phosphorus system processing stabilizers The pellet (hereinafter, the polyamide 6/66/12 composition is known as (B2-2)) of object.
The manufacture of polyamide 6/66/12 composition (B2-3)
In the manufacture of polyamide 6/66/12 composition (B2-1), do not use polyamide 610 (b-3), in addition to this, benefit With method identical with polyamide 6/manufacture of 66/12 composition (B2-1), obtain relative to polyamide 6/66,/12 80 matter Total 100 mass parts for measuring %, 15 mass % of modified impact material, 5 mass % of plasticizer, comprising 0.8 mass parts of antioxidant, Polyamide 6/66/12 composition pellet of 0.2 mass parts of phosphorus system processing stabilizers is (hereinafter, by the polyamide 6/66/12 combination Object is known as (B2-3)).
The manufacture of polyamide 6/66/12 composition (B2-4)
In the manufacture of polyamide 6/66/12 composition (B2-1), polyamide 610 (b-3), modified impact material are not used And plasticizer, in addition to this, using method identical with polyamide 6/manufacture of 66/12 composition (B2-1), obtain relative to Polyamide 6/66,/12 100 mass %, the polyamide comprising 0.8 mass parts of antioxidant, 0.2 mass parts of phosphorus system processing stabilizers The pellet (hereinafter, the polyamide 6/66/12 composition is known as (B2-4)) of 6/66/12 composition.
The manufacture of polyamide 6/12 (b-5)
In the manufacture of polyamide 6/66/12 (b-2), by caprolactam 16.2kg, 1,6- hexamethylene diamine and decanedioic acid etc. 50 mass % aqueous solution 5.0kg and 12 amino dodecanoic acid 2.5kg of molar salt are changed to caprolactam 16.2kg, 12- In addition to this aminododecanoic acid 4.4kg, additional water 2kg utilize side identical with the manufacture of polyamide 6/66/12 (b-2) Method, obtain relative viscosity be 3.86 polyamide 6/12 (hexanoyl amine unit/dodecanoyl amine unit=80/20 mass %) (with Under, which is known as (b-5)).
The manufacture of polyamide 6/12 compositions (B2-5)
In the manufacture of polyamide 6/66/12 composition (B2-1), polyamide 6/66/12 (b-2) is changed to polyamide 6/12 (b-5), do not use polyamide 610 (b-3), in addition to this, using with the manufacture of polyamide 6/66/12 composition (B2-1) Identical method is obtained relative to polyamide 6/12 80 mass %, 15 mass % of modified impact material, plasticizer 5 mass % Total 100 mass parts, polyamide 6/12 compositions comprising 0.8 mass parts of antioxidant, 0.2 mass parts of phosphorus system processing stabilizers Pellet (hereinafter, by the polyamide 6/12 compositions be known as (B2-5)).
EVOH (C-1): Japan's synthesis Chemical Co., Ltd. system, SOARNOL DC3203, ethylene contents are 32 moles of %, soaps Change degree is 99 moles of % or more
The manufacture of semiaromatic polyamide composition (d1-1)
It is 8- octamethylenediamine 2.374kg (15.0 moles), right by 1,9-nonamethylene diamine 2.374kg (15.0 moles) and 2- methyl-1 Phthalic acid 4.984kg (30.0 moles), benzoic acid 65.9g (0.54 mole), sodium hypophosphite monohydrate 10.2g (relative to Raw material is that 0.1 mass %) and distilled water 6.0L are put into autoclave, carries out nitrogen displacement.It is stirred 30 minutes with 100 DEG C, consumption Internal temperature is warming up to 210 DEG C in 2 hours by expense.At this point, autoclave is boosted to 2.2MPa.Keep the state sustained response 1 small Shi Hou is warming up to 230 DEG C, thereafter by temperature keep to 230 DEG C 2 hours, gently remove vapor, on one side by pressure keep to 2.2MPa makes its reaction on one side.Then, 30 minutes are expended by pressure reduction to 1.0MPa, and then reacted 1 hour, to obtain Prepolymer.It is dried under reduced pressure 12 hours with 100 DEG C, until being crushed to 2mm size below, in 230 DEG C, 0.013kPa Lower solid phase 8 hours, thus obtain fusing point is 265 DEG C, relative viscosity is 2.38 semiaromatic polyamide composition (polyamide 9T/ M8T=50/50 moles of %) (hereinafter, the semiaromatic polyamide composition is known as (d1-1)).
The manufacture of semiaromatic polyamide composition composition (D1-1)
The maleic anhydride modified ethylene/propylene as modified impact material is pre-mixed in semiaromatic polyamide composition (d1-1) Alkene copolymer (JSR Corp.'s system, JSR T7761P), the bis- [3- (3- tert-butyl -5- first of triethylene glycol as antioxidant Base -4- hydroxy phenyl) propionic ester] (BASF JAPAN corporation, IRGANOX245) and as the three of phosphorus system processing stabilizers (2,4- di-tert-butyl-phenyl) phosphite ester (BASF JAPAN corporation, IRGAFOS168), and supply mixed to twin-screw melting Mill (Corporation Japan Steel Works' system, model: TEX44) will with 300 DEG C of progress melting mixings from 240 DEG C of barrel temperature It after molten resin is extruded into strand form, is conducted into sink, cool down, cut, be dried in vacuo, obtain relative to half virtue Total 100 mass parts of fragrant 90 mass % of polyamide, 10 mass % of modified impact material, comprising 0.8 mass parts of antioxidant, The pellet of the semiaromatic polyamide composition composition of 0.2 mass parts of phosphorus system processing stabilizers is (hereinafter, by the semiaromatic polyamide composition group It closes object and is known as (D1-1)).
The manufacture of semiaromatic polyamide composition (d1-2)
In the manufacture of semiaromatic polyamide composition (d1-1), by 1,9- nonamethylene diamine 2.374kg (15.0 moles) and 2- methyl- 1,8- octamethylenediamine 2.374kg (15.0 moles) is changed to 1,9-nonamethylene diamine 4.036kg (25.5 moles), 2- methyl-1,8- pungent two Solid phase polymerization temperature is changed to 250 DEG C from 230 by amine 0.712kg (4.5 moles), in addition to this, using with semi-aromatic polyamides The identical method of manufacture of amine (d1-1), obtains the semiaromatic polyamide composition (polyamides that fusing point is 305 DEG C, relative viscosity is 2.34 9T/M8T=85/15 moles of % of amine) (hereinafter, the semiaromatic polyamide composition is known as (d1-2)).
The manufacture of semiaromatic polyamide composition composition (D1-2)
In the manufacture of semiaromatic polyamide composition composition (D1-1), semiaromatic polyamide composition (d1-1) is changed to (d1- 2) barrel temperature, is changed to 330 DEG C from 300 DEG C, in addition to this, utilizes the system with semiaromatic polyamide composition composition (D1-1) Identical method is made, total 100 matter relative to 90 mass % of semiaromatic polyamide composition, 10 mass % of modified impact material are obtained Measure part, the grain of the semiaromatic polyamide composition composition comprising 0.8 mass parts of antioxidant, 0.2 mass parts of phosphorus system processing stabilizers Material (hereinafter, the semiaromatic polyamide composition composition is known as (D1-2)).
The manufacture of semiaromatic polyamide composition (d1-3)
In the manufacture of semiaromatic polyamide composition (d1-1), terephthalic acid (TPA) 4.984kg (30.0 moles) is changed to 2, 6- naphthalenedicarboxylic acid 6.486kg (30.0 moles) in addition to this utilizes side identical with the manufacture of semiaromatic polyamide composition (d1-1) Method obtains the semiaromatic polyamide composition (9N/M8N=50/50 moles of % of polyamide) that fusing point is 275 DEG C, relative viscosity is 2.37 (hereinafter, the semiaromatic polyamide composition is known as (d1-3)).
The manufacture of semiaromatic polyamide composition composition (D1-3)
In the manufacture of semiaromatic polyamide composition composition (D1-1), semiaromatic polyamide composition (d1-1) is changed to (d1- 3) barrel temperature, is changed to 310 DEG C from 300 DEG C, in addition to this, utilizes the system with semiaromatic polyamide composition composition (D1-1) Identical method is made, total 100 matter relative to 90 mass % of semiaromatic polyamide composition, 10 mass % of modified impact material are obtained Measure part, the grain of the semiaromatic polyamide composition composition comprising 0.8 mass parts of antioxidant, 0.2 mass parts of phosphorus system processing stabilizers Material (hereinafter, the semiaromatic polyamide composition composition is known as (D1-3)).
The manufacture of semiaromatic polyamide composition (d1-4)
In the manufacture of semiaromatic polyamide composition (d1-1), by 1,9- nonamethylene diamine 2.374kg (15.0 moles) and 2- methyl- 1,8- octamethylenediamine 2.374kg (15.0 moles) is changed to 1,10- decamethylene diamine 5.169kg (30.0 moles), by solid phase polymerization temperature 260 DEG C are changed to from 230 DEG C, in addition to this, using method identical with the manufacture of semiaromatic polyamide composition (d1-1), is melted The semiaromatic polyamide composition (10T=100 moles of % of polyamide) that point is 315 DEG C, relative viscosity is 2.33 is (hereinafter, should half virtue Fragrant polyamide is known as (d1-4)).
The manufacture of semiaromatic polyamide composition composition (D1-4)
In the manufacture of semiaromatic polyamide composition composition (D1-1), semiaromatic polyamide composition (d1-1) is changed to (d1- 4) barrel temperature, is changed to 340 DEG C from 300 DEG C, in addition to this, utilizes the system with semiaromatic polyamide composition composition (D1-1) Identical method is made, total 100 matter relative to 90 mass % of semiaromatic polyamide composition, 10 mass % of modified impact material are obtained Measure part, the grain of the semiaromatic polyamide composition composition comprising 0.8 mass parts of antioxidant, 0.2 mass parts of phosphorus system processing stabilizers Material (hereinafter, the semiaromatic polyamide composition composition is known as (D1-4)).
The manufacture of semiaromatic polyamide composition (d1-5)
In the manufacture of semiaromatic polyamide composition (d1-4), by 1,10- decamethylene diamine 5.169kg (30.0 moles), to benzene two Formic acid 4.984kg (30.0 moles) is changed to 1,10- decamethylene diamine 3.101kg (18.0 moles), terephthalic acid (TPA) 2.990kg (18.0 moles) and 11- amino undecanoic acid 2.416kg (12.0 moles), is changed to 200 from 260 DEG C for solid phase polymerization temperature DEG C, in addition to this, using method identical with the manufacture of semiaromatic polyamide composition (d1-4), obtains fusing point and be 255 DEG C, glue relatively The semiaromatic polyamide composition copolymer (10T/11=60/40 moles of % of polyamide) that degree is 2.34 is (hereinafter, by the semiaromatic adoption Amide copolymer is known as (d1-5)).
The manufacture of semiaromatic polyamide composition composition (D1-5)
In the manufacture of semiaromatic polyamide composition composition (D1-1), semiaromatic polyamide composition (d1-1) is changed to (d1- 5) barrel temperature, is changed to 290 DEG C from 300 DEG C, in addition to this, utilizes the system with semiaromatic polyamide composition composition (D1-1) Identical method is made, total 100 matter relative to 90 mass % of semiaromatic polyamide composition, 10 mass % of modified impact material are obtained Measure part, the grain of the semiaromatic polyamide composition composition comprising 0.8 mass parts of antioxidant, 0.2 mass parts of phosphorus system processing stabilizers Material (hereinafter, the semiaromatic polyamide composition composition is known as (D1-5)).
The manufacture of semiaromatic polyamide composition (d1-6)
In the manufacture of semiaromatic polyamide composition (d1-4), terephthalic acid (TPA) 4.984kg (30.0 moles) is changed to pair Phthalic acid 3.324kg (20.0 moles), decanedioic acid 2.020kg (9.99 moles), solid phase polymerization temperature is changed to from 260 DEG C 220 DEG C, in addition to this, using method identical with the manufacture of semiaromatic polyamide composition (d1-4), obtaining fusing point is 279 DEG C, phase To viscosity be 2.37 semiaromatic polyamide composition copolymer (10T/1010=67/33 moles of % of polyamide) (hereinafter, should be partly fragrant Fragrant polyamide copolymer is known as (d1-6)).
The manufacture of semiaromatic polyamide composition composition (D1-6)
In the manufacture of semiaromatic polyamide composition composition (D1-1), semiaromatic polyamide composition (d1-1) is changed to (d1- 6) barrel temperature, is changed to 310 DEG C from 300 DEG C, in addition to this, utilizes the system with semiaromatic polyamide composition composition (D1-1) Identical method is made, total 100 matter relative to 90 mass % of semiaromatic polyamide composition, 10 mass % of modified impact material are obtained Measure part, the grain of the semiaromatic polyamide composition composition comprising 0.8 mass parts of antioxidant, 0.2 mass parts of phosphorus system processing stabilizers Material (hereinafter, the semiaromatic polyamide composition composition is known as (D1-6)).
The manufacture of semiaromatic polyamide composition (d1-7)
In the manufacture of semiaromatic polyamide composition (d1-1), solid state polymerization time was changed to 4 hours from 8 hours, removes this Except, using method identical with the manufacture of semiaromatic polyamide composition (d1-1), obtain that fusing point is 265 DEG C, relative viscosity is 2.16 semiaromatic polyamide composition (polyamide 9T/M8T=50/50 moles of %) is (hereinafter, the semiaromatic polyamide composition is known as (d1-7))。
The manufacture of electric conductivity semiaromatic polyamide composition composition (D1-7)
In the manufacture of semiaromatic polyamide composition composition (D1-1), semiaromatic polyamide composition (d1-1) is changed to (d1- 7), maleic anhydride modified ethylene/propene copolymer (JSR Corp.'s system, JSR T7761P) is changed to maleic anhydride modified Ethylene/1-butene copolymer (Mitsui Chemicals, Inc's system, TAFMER MH5010) and Ethylene/1-butene copolymer (three wells Learn Co. Ltd. system, TAFMER A-0550), use carbon nanotube (Nanocyl corporation, NC7000) as electroconductive stuffing, Barrel temperature is changed to 320 DEG C from 300 DEG C, in addition to this, utilizes the manufacture with semiaromatic polyamide composition composition (D1-1) Identical method is obtained relative to 75 mass % of semiaromatic polyamide composition, 20 mass % of modified impact material, electroconductive stuffing 5 Total 100 mass parts of quality % include 0.8 mass parts of antioxidant, the electric conductivity of 0.2 mass parts of phosphorus system processing stabilizers half The pellet (hereinafter, the electric conductivity semiaromatic polyamide composition composition is known as (D1-7)) of aromatic polyamide composition.
The manufacture of semiaromatic polyamide composition (d1-8)
In the manufacture of semiaromatic polyamide composition (d1-4), by 1,10- decamethylene diamine 5.169kg (30.0 moles), to benzene two Formic acid 4.984kg (30.0 moles) is changed to 1,6- hexamethylene diamine 3.718kg (32.0 moles), terephthalic acid (TPA) 3.240kg (19.5 Mole), M-phthalic acid 1.246kg (7.5 moles) and adipic acid 0.438kg (3.0 moles), in addition to this, using with half virtue The identical method of manufacture of fragrant polyamide (d1-4), obtains the semi-aromatic polyamides that fusing point is 315 DEG C, relative viscosity is 2.38 Amine (T/6I/66=65/25/10 moles of % of polyamide 6) (hereinafter, the semiaromatic polyamide composition is known as (d1-8)).
The manufacture of semiaromatic polyamide composition composition (D1-8)
In the manufacture of semiaromatic polyamide composition composition (D1-1), semiaromatic polyamide composition (d1-1) is changed to (d1- 8) barrel temperature, is changed to 340 DEG C from 300 DEG C, in addition to this, utilizes the system with semiaromatic polyamide composition composition (D1-1) Identical method is made, total 100 matter relative to 90 mass % of semiaromatic polyamide composition, 10 mass % of modified impact material are obtained Measure part, the grain of the semiaromatic polyamide composition composition comprising 0.8 mass parts of antioxidant, 0.2 mass parts of phosphorus system processing stabilizers Material (hereinafter, the semiaromatic polyamide composition composition is known as (D1-8)).
The manufacture of semiaromatic polyamide composition (d2-1)
It is imported to having blender, thermometer, torquemeter, pressure gauge, the material pouring inlet for being in series with diaphragm pump, nitrogen Decanedioic acid is put into the pressure vessel that mouth, the internal volume for bleeding off pressure mouth, pressure-regulating device and polymer liberation port are 40 liters 6.068kg (30.0 moles), calcium hypophosphite 8.50g (0.049 mole) and sodium acetate 2.19g (0.025 mole) are with purity 99.9999% nitrogen after the internal pressurization to 0.3MPa of pressure vessel, will then discharge nitrogen to normal pressure, which is repeated It 5 times, after carrying out nitrogen displacement, is directed in system and heats up while stirring in envelope pressure.In turn, in a small amount of stream of nitrogen gas Under be warming up to 190 DEG C after, under stiring expend 160 minutes dropwise addition p dimethylamine 4.086kg (30.0 moles).It therebetween, will be anti- It answers the internal pressure of system to control to 0.5MPa, internal temperature is made continuously to be warming up to 295 DEG C.In addition, will be added dropwise to benzene two The water distillated while methylamine is removed by segregator and cooler to outside system.After the completion of dropwise addition of p dimethylamine, expend Until 60 minutes are depressurized to normal pressure, the temperature in container is maintained at 300 DEG C, and sustained response 10 minutes therebetween.It thereafter, will be anti- Until answering the internal pressure of system to be decompressed to 79kPa, 40 minutes melt polymerizations are persistently carried out.Thereafter, stop stirring, it will It is forced into 0.2MPa with nitrogen in system, condensation polymer is become band from the taking-up of the outlet of pressure vessel lower part.Band-like polycondensation Object cools down immediately, and water cooled band resin is by pelletizer pelletizing batch, thereafter, is dried under reduced pressure, to obtain fusing point For 281,291 DEG C (with 2 fusing points), semiaromatic polyamide composition that relative viscosity is 2.47, (polyamide PXD10=100 rubs You are %) (hereinafter, the semiaromatic polyamide composition is known as (d2-1)).
The manufacture of semiaromatic polyamide composition composition (D2-1)
In the manufacture of semiaromatic polyamide composition composition (D1-1), semiaromatic polyamide composition (d1-1) is changed to (d2- 1) barrel temperature, is changed to 320 DEG C from 300 DEG C, in addition to this, utilizes the system with semiaromatic polyamide composition composition (D1-1) Identical method is made, total 100 matter relative to 90 mass % of semiaromatic polyamide composition, 10 mass % of modified impact material are obtained Measure part, the grain of the semiaromatic polyamide composition composition comprising 0.8 mass parts of antioxidant, 0.2 mass parts of phosphorus system processing stabilizers Material (hereinafter, the semiaromatic polyamide composition composition is known as (D2-1)).
The manufacture of semiaromatic polyamide composition (d2-2)
In the manufacture of semiaromatic polyamide composition (d2-1), decanedioic acid 6.068kg (30.0 moles) is changed to azelaic acid 5.647kg (30.0 moles) in addition to this using method identical with the manufacture of semiaromatic polyamide composition (d2-1), is melted The semiaromatic polyamide composition (PXD9=100 moles of % of polyamide) that point is 270 DEG C, relative viscosity is 2.45 is (hereinafter, should half virtue Fragrant polyamide is known as (d2-2)).
The manufacture of semiaromatic polyamide composition composition (D2-2)
In the manufacture of semiaromatic polyamide composition composition (D2-1), semiaromatic polyamide composition (d2-1) is changed to (d2- 2) barrel temperature, is changed to 310 DEG C from 320 DEG C, in addition to this, utilizes the system with semiaromatic polyamide composition composition (D2-1) Identical method is made, total 100 matter relative to 90 mass % of semiaromatic polyamide composition, 10 mass % of modified impact material are obtained Measure part, the grain of the semiaromatic polyamide composition composition comprising 0.8 mass parts of antioxidant, 0.2 mass parts of phosphorus system processing stabilizers Material (hereinafter, the semiaromatic polyamide composition composition is known as (D2-2)).
The manufacture of semiaromatic polyamide composition (d2-3)
In the manufacture of semiaromatic polyamide composition (d2-1), between p dimethylamine 4.086kg (30.0 moles) is changed to Polymerization temperature is changed to 250 DEG C from 300 DEG C by benzene dimethylamine 4.086kg (30.0 moles), in addition to this, utilization and semiaromatic The identical method of manufacture of polyamide (d2-1), obtains the semiaromatic polyamide composition that fusing point is 191 DEG C, relative viscosity is 2.46 (MXD10=100 moles of % of polyamide) (hereinafter, the semiaromatic polyamide composition is known as (d2-3)).
The manufacture of semiaromatic polyamide composition composition (D2-3)
In the manufacture of semiaromatic polyamide composition composition (D2-1), semiaromatic polyamide composition (d2-1) is changed to (d2- 3) barrel temperature, is changed to 240 DEG C from 320 DEG C, in addition to this, utilizes the system with semiaromatic polyamide composition composition (D2-1) Identical method is made, total 100 matter relative to 90 mass % of semiaromatic polyamide composition, 10 mass % of modified impact material are obtained Measure part, the grain of the semiaromatic polyamide composition composition comprising 0.8 mass parts of antioxidant, 0.2 mass parts of phosphorus system processing stabilizers Material (hereinafter, the semiaromatic polyamide composition composition is known as (D2-3)).
The manufacture of semiaromatic polyamide composition (d2-4)
In the manufacture of semiaromatic polyamide composition (d2-3), decanedioic acid 6.068kg (30.0 moles) is changed to dodecane Polymerization temperature is changed to 240 DEG C from 250 DEG C by diacid 6.488kg (30.0 moles), in addition to this, using with semiaromatic adoption It is (poly- to obtain the semiaromatic polyamide composition that fusing point is 175 DEG C, relative viscosity is 2.40 for the identical method of manufacture of amide (d2-3) MXD12=100 moles of % of amide) (hereinafter, the semiaromatic polyamide composition is known as (d2-4)).
The manufacture of semiaromatic polyamide composition composition (D2-4)
In the manufacture of semiaromatic polyamide composition composition (D2-1), semiaromatic polyamide composition (d2-1) is changed to (d2- 4) barrel temperature, is changed to 230 DEG C from 320 DEG C, in addition to this, utilizes the system with semiaromatic polyamide composition composition (D2-1) Identical method is made, total 100 matter relative to 90 mass % of semiaromatic polyamide composition, 10 mass % of modified impact material are obtained Measure part, the grain of the semiaromatic polyamide composition composition comprising 0.8 mass parts of antioxidant, 0.2 mass parts of phosphorus system processing stabilizers Material (hereinafter, the semiaromatic polyamide composition composition is known as (D2-4)).
The manufacture of semiaromatic polyamide composition (d2-5)
In the manufacture of semiaromatic polyamide composition (d2-1), between p dimethylamine 4.086kg (30.0 moles) is changed to The hybrid diamine 4.086kg (30.0 moles) of benzene dimethylamine and the 7:3 of p dimethylamine, polymerization temperature is changed to from 300 DEG C 260 DEG C, in addition to this, using method identical with the manufacture of semiaromatic polyamide composition (d2-1), obtaining fusing point is 215 DEG C, phase To viscosity be 2.45 semiaromatic polyamide composition (MXD10/PXD10=70/30 moles of % of polyamide) (hereinafter, by the semiaromatic Polyamide is known as (d2-5)).
The manufacture of semiaromatic polyamide composition composition (D2-5)
In the manufacture of semiaromatic polyamide composition composition (D2-1), semiaromatic polyamide composition (d2-1) is changed to (d2- 5) barrel temperature, is changed to 250 DEG C from 320 DEG C, in addition to this, utilizes the system with semiaromatic polyamide composition composition (D2-1) Identical method is made, total 100 matter relative to 90 mass % of semiaromatic polyamide composition, 10 mass % of modified impact material are obtained Measure part, the grain of the semiaromatic polyamide composition composition comprising 0.8 mass parts of antioxidant, 0.2 mass parts of phosphorus system processing stabilizers Material (hereinafter, the semiaromatic polyamide composition composition is known as (D2-5)).
The manufacture of semiaromatic polyamide composition (d2-6)
In the manufacture of semiaromatic polyamide composition (d2-4), m-xylene diamine 4.086kg (30.0 moles) is changed to 2, Polymerization temperature is changed to 300 DEG C from 240 DEG C by bis- (amino methyl) the naphthalene 5.588kg of 6- (30.0 moles), in addition to this, is utilized Method identical with the manufacture of semiaromatic polyamide composition (d2-4), obtains the semiaromatic that fusing point is 272 DEG C, relative viscosity is 2.33 Polyamide (polyamide 2,6-BAN12=100 moles of %) (hereinafter, the semiaromatic polyamide composition is known as (d2-6)).
The manufacture of semiaromatic polyamide composition composition (D2-6)
In the manufacture of semiaromatic polyamide composition composition (D2-1), semiaromatic polyamide composition (d2-1) is changed to (d2- 6) barrel temperature, is changed to 310 DEG C from 320 DEG C, in addition to this, utilizes the system with semiaromatic polyamide composition composition (D2-1) Identical method is made, total 100 matter relative to 90 mass % of semiaromatic polyamide composition, 10 mass % of modified impact material are obtained Measure part, the grain of the semiaromatic polyamide composition composition comprising 0.8 mass parts of antioxidant, 0.2 mass parts of phosphorus system processing stabilizers Material (hereinafter, the semiaromatic polyamide composition composition is known as (D2-6)).
The manufacture of semiaromatic polyamide composition (d2-7)
In the manufacture of semiaromatic polyamide composition (d2-1), between p dimethylamine 4.086kg (30.0 moles) is changed to Benzene dimethylamine 4.086kg (30.0 moles), decanedioic acid 6.068kg (30.0 moles) is changed to adipic acid 4.384kg, and (30.0 rub You), polymerization temperature is changed to 275 DEG C from 300 DEG C, in addition to this, utilizes the manufacture phase with semiaromatic polyamide composition (d2-1) Same method, obtaining the semiaromatic polyamide composition that fusing point is 243 DEG C, relative viscosity is 2.45, (polyamide MXD6=100 rubs You are %) (hereinafter, the semiaromatic polyamide composition is known as (d2-7)).
The manufacture of semiaromatic polyamide composition composition (D2-7)
In the manufacture of semiaromatic polyamide composition composition (D2-1), semiaromatic polyamide composition (d2-1) is changed to (d2- 7) barrel temperature, is changed to 280 DEG C from 320 DEG C, in addition to this, utilizes the system with semiaromatic polyamide composition composition (D2-1) Identical method is made, total 100 matter relative to 90 mass % of semiaromatic polyamide composition, 10 mass % of modified impact material are obtained Measure part, the grain of the semiaromatic polyamide composition composition comprising 0.8 mass parts of antioxidant, 0.2 mass parts of phosphorus system processing stabilizers Material (hereinafter, the semiaromatic polyamide composition composition is known as (D2-7)).
Containing fluorine system polymer (E)
Manufacture containing fluorine system polymer (E-1)
The polymerization tank with blender that internal volume is 100L is de-gassed, ten trifluorohexane 92.1kg of 1- hydrogen, 1 are put into, The chloro- 1,1,2,2,3- pentafluoropropane 16.3kg of 3- bis-, (perfluoro-ethyl) ethylene CH2=CH (CF2)2F73g, itaconic anhydride (IAH) 10.1g is pressed into tetrafluoroethene (TFE) 9.6kg, ethylene (E) 0.7kg, 66 DEG C will be warming up in polymerization tank, investment is drawn as polymerization Send out the chloro- 1,1,2,2,3- pentafluoropropane solution 433cm of 1,3- bis- of the 1 mass % of tert-butyl hydroperoxide pivalate of agent3, start Polymerization.The monomer mixed gas of TFE/E:60/40 (molar ratio) is continuously put into, so that the pressure in polymerization reaches constant.This Outside, continuously putting into relative to the total mole number of the TFE and E that put into polymerization is (the perfluor second for being equivalent to the amount of 2.0 moles of % Base) ethylene and be equivalent to 0.5 mole of % amount IAH.After polymerization starts 5.5 hours, monomer mixed gas is put into At the time of 8.0kg, IAH 63g, the internal temperature of polymerization tank is reduced to room temperature, is purged and makes pressure normal pressure.By institute It obtains putting into containing fluorine system polymer to the 200L equipped with water 75.0kg for pulp-like to be granulated in slot, then, heat up while stirring To 105 DEG C, it is granulated while distilling removal solvent.Gained granules are 5 hours dry at 150 DEG C, to obtain 8.3kg Contain fluorine system polymer.
In the composition containing fluorine system polymer, the polymerized unit based on the TFE/polymerized unit based on E/be based on CH2=CH (CF2)2The polymerized unit of F/polymerized unit=58.5/39.0/2.0/0.5 (mole %) based on IAH, fusing point are 240 DEG C.Make With extruder, which is melted with the residence time of 280 DEG C, 2 minutes, to obtain the pellet containing fluorine system polymer (hereinafter, this is known as (E-1) containing fluorine system polymer).
Electric conductivity contains the manufacture of fluorine system polymer (E-2)
100 mass parts of fluorine system polymer (E-1) will be contained and 13 mass parts of carbon black (electrochemically Co. Ltd. system) are mixed in advance It closes, and supplies into twin-screw melting mixing machine (Toshiba Machinery Co., Ltd.'s system, model: TEM-48S), from barrel temperature 240 DEG C rise with 300 DEG C of progress melting mixings, after molten resin is extruded into strand form, be conducted into sink, by the stock of ejection Line water cooling cuts off strand with pelletizer, is dried 10 hours to remove moisture removal with 120 DEG C of drying machine, obtains electric conductivity and contain The pellet (hereinafter, the electric conductivity is known as (E-2) containing fluorine system polymer) of fluorine system polymer.
Manufacture containing fluorine system polymer (E-3)
Containing fluorine system polymer (E-1) manufacture in, do not put into itaconic anhydride (IAH), in addition to this, using with contain fluorine system The identical method of manufacture of polymer (E-1), obtain 7.6kg contains fluorine system polymer.
In the composition containing fluorine system polymer, the polymerized unit based on the TFE/polymerized unit based on E/be based on CH2=CH (CF2)2Polymerized unit=58.8/39.2/2.0 (mole %) of F, fusing point are 242 DEG C.By the granules using extruder with 280 DEG C, 2 minutes residence times melted, to obtain the pellet containing fluorine system polymer (hereinafter, this is claimed containing fluorine system polymer For (E-3)).
Electric conductivity contains the manufacture of fluorine system polymer (E-4)
In manufacture of the electric conductivity containing fluorine system polymer (E-2), fluorine system polymer (E-1) will be contained and be altered to (E-3), and remove this Except, containing the identical method of the manufacture of fluorine system polymer (E-2), grain of the electric conductivity containing fluorine system polymer is obtained using with electric conductivity Material (hereinafter, the electric conductivity is known as (E-4) containing fluorine system polymer).
Manufacture containing fluorine system polymer (E-5)
The polymerization tank with blender that internal volume is 100L is de-gassed, 1,3- bis- chloro- 1,1,2,2,3- five fluorine are put into Propane 42.5kg, CF2=CFOCF2CF2CF3(perfluor (propyl vinyl ether): PPVE), 1,1,2,4,4,5,5,6,6,6- ten Fluoro- 3- oxa- hex- 1- alkene) 2.13kg, hexafluoropropene (HFP) 51.0kg.Then, 50 DEG C will be warming up in polymerization tank, investment four Vinyl fluoride (TFE) 4.25kg and by boost in pressure to 1.0MPa/G.As polymerization initiator solution, peroxidating (perfluor fourth is put into Acyl) 0.3 mass % the chloro- 1,1,2,2,3- pentafluoropropane solution 340cm of 1,3- bis-3, start to polymerize, put within every 10 minutes later Polymerization initiator solution 340cm3.TFE is continuously put into the course of the polymerization process, so that pressure remains 1.0MPa/G.In addition, It continuously puts into relative to the 5- bornylene -2,3- two that the molal quantity of the TFE put into polymerization is the amount for being equivalent to 0.1 mole of % The chloro- 1,1,2,2,3- pentafluoropropane solution of 1,3- bis- of 0.3 mass % of carboxylic acid anhydrides (NAH).After polymerization starts 5 hours, put into At the time of TFE8.5kg, the internal temperature of polymerization tank is reduced to room temperature, while carrying out purging until normal pressure.Gained is starched Putting into containing fluorine system polymer to the 200L equipped with water 75.0kg for material shape is granulated in slot, then, is warming up to 105 while stirring DEG C, it is granulated while distilling removal solvent.Gained granules are 5 hours dry at 150 DEG C, to obtain containing for 7.5kg The granules of fluorine system polymer.
In the composition containing fluorine system polymer, the polymerized unit based on the TFE/polymerized unit based on PPVE/based on HFP's Polymerized unit/polymerized unit=91.2/1.5/7.2/0.1 (mole %) based on NAH, fusing point are 262 DEG C.Using extruder, The granules are melted with the residence time of 300 DEG C, 2 minutes, to obtain the pellet containing fluorine system polymer (hereinafter, will This contains fluorine system polymer and is known as (E-5)).
Electric conductivity contains the manufacture of fluorine system polymer (E-6)
In manufacture of the electric conductivity containing fluorine system polymer (E-2), fluorine system polymer (E-1) will be contained and be changed to (E-5), by charcoal Black 13 mass parts are changed to 11 mass parts, and barrel temperature is changed to 320 DEG C from 300 DEG C, in addition to this, is contained using with electric conductivity The identical method of manufacture of fluorine system polymer (E-2) obtains pellet of the electric conductivity containing fluorine system polymer (hereinafter, by the electric conductivity It is known as (E-6) containing fluorine system polymer).
Manufacture containing fluorine system polymer (E-7)
In the manufacture containing fluorine system polymer (E-5), 0.3 mass % of 5- bornylene -2,3- dicarboxylic anhydride (NAH) is not put into 1,3- bis- chloro- 1,1,2,2,3- pentafluoropropane solution, in addition to this, using with containing the manufacture of fluorine system polymer (E-5) it is identical Method, obtain 7.6kg containing fluorine system polymer.
In the composition containing fluorine system polymer, the polymerized unit based on the TFE/polymerized unit based on PPVE/based on HFP's Polymerized unit=91.5/1.5/7.0 (mole %), fusing point are 257 DEG C.Using extruder, by the granules with 300 DEG C, 2 minutes Residence time melted, obtain the pellet (hereinafter, this is known as (E-7) containing fluorine system polymer) containing fluorine system polymer.
Manufacture containing fluorine system polymer (E-8)
The pure water 51.5kg of demineralization is put into the stirring-type polymerization tank for the jacketed that can accommodate water 174kg, it will After inner space is sufficiently displaced from pure nitrogen gas, vacuumize to exclude nitrogen.Then, octafluorocyclobutane 40.6kg, trifluoro chlorine are pressed into Ethylene (CTFE) 1.6kg, tetrafluoroethene (TFE) 4.5kg, perfluor (propyl vinyl ether) (PPVE) 2.8kg.As chain-transferring agent Addition normal propyl alcohol 0.090kg starts to stir the temperature was then adjusted to 35 DEG C.Two positive third as polymerization initiator are added thereto The methanol solution 0.44kg of 50 mass % of base peroxy dicarbonate, starts to polymerize.In the course of the polymerization process, additional input is prepared into Become the mix monomer of same composition with desired copolymer group and polymerize, so that pressure is maintained 0.66MPa in slot, so The residual gas in slot is discharged afterwards, takes out polymer generated, is cleaned with the pure water of demineralization, make it dry and obtain Contain fluorine system polymer to 30.5kg nodular powder.
In the composition of the fluorine system polymer, with the polymerized unit based on CTFE/polymerized unit based on TFE/be based on PPVE Polymerized unit molar ratio computing be 24.4/73.1/2.5, the carbonate end base from polymerization initiator of fluorine system polymer The quantity of group is 170.In addition, fusing point is 241 DEG C.Using extruder, by the granules with 290 DEG C, 2 minutes residence times It is melted, obtains the pellet (hereinafter, this is known as (E-8) containing fluorine system polymer) containing fluorine system polymer.
Electric conductivity contains the manufacture of fluorine system polymer (E-9)
In manufacture of the electric conductivity containing fluorine system polymer (E-6), fluorine system polymer (E-5) will be contained and be changed to (E-8), and remove this Except, containing the identical method of the manufacture of fluorine system polymer (E-6), grain of the electric conductivity containing fluorine system polymer is obtained using with electric conductivity Material (hereinafter, the electric conductivity is known as (E-9) containing fluorine system polymer).
Manufacture containing fluorine system polymer (E-10)
In the manufacture containing fluorine system polymer (E-8), the first of 50 mass % of diη-propyl peroxy dicarbonate is not put into In addition to this alcoholic solution using method identical with the manufacture of fluorine system polymer (E-8) is contained, obtains the poly- containing fluorine system of 29.8kg Close object.
In the composition containing fluorine system polymer, with the polymerized unit based on CTFE ,/polymerized unit based on TFE/is based on The molar ratio computing of the polymerized unit of PPVE is 24.4/73.1/2.5, and fusing point is 241 DEG C.Using extruder, by the granules with 290 DEG C, 2 minutes residence times melted, obtain the pellet containing fluorine system polymer (hereinafter, this is claimed containing fluorine system polymer For (E-10)).
Embodiment 1
Use above-mentioned 12 composition of polyamide (A-1) shown, polyamide 6 composition (B1-1), polyamide 6/66/12 group Object (B2-1), EVOH (C-1) and semiaromatic polyamide composition composition (D1-1) are closed, Plabor (plastics engineering research institute strain is utilized Formula commercial firm system) 5 layers of pipe forming machine, make respectively (A-1) with 250 DEG C of extrusion temperature, make (B1-1) with 260 DEG C of extrusion temperature, Make (B2-1) with 260 DEG C of extrusion temperature, make (C-1) with 220 DEG C of extrusion temperature, make (D1-1) with 300 DEG C of extrusion temperature It is melted, collaborates the molten resin of discharge with interflow device, and be configured to stacking tubular body.Then, using for controlling ruler Very little stock mould is cooled down and is removed, and (a) layer (outermost layer) formed by (A-1), (b) layer formed by (B2-1) is made (outer layer), (c) layer (middle layer) formed by (C-1), are formed (the b ') layer (internal layer 1) formed by (B1-1) by (D1-1) (d) it when layer (innermost layer), obtains layer and is configured to (a)/(b)/(c)/(b ')/(d)=0.35/0.15/0.10/0.25/0.15mm And the stacking pipe that internal diameter is 6mm, outer diameter is 8mm.The physical property measurement result of the stacking pipe is shown in table 1.
Embodiment 2
In embodiment 1, polyamide 6 composition (B1-1) is changed to polyamide 6/66/12 composition (B2-1), except this it Outside, using method same as Example 1, (a) layer (outermost layer) formed by (A-1), (b) layer formed by (B2-1) is made When (outer layer, internal layer 1), (c) layer (middle layer) formed by (C-1), (d) layer (innermost layer) formed by (D1-1), layer is obtained It is configured to (a)/(b)/(c)/(b)/(d)=0.35/0.15/0.10/0.25/0.15mm and internal diameter is 6mm, outer diameter is 8mm's Stacking pipe.The physical property measurement result of the stacking pipe is shown in table 1.
Embodiment 3
Use above-mentioned 12 composition of polyamide (A-2) shown, polyamide 6 composition (B1-1), EVOH (C-1) He Banfang Fragrant polyamide composition (D1-1) is made respectively using 6 layers of pipe forming machine of Plabor (plastics engineering research institute Co. Ltd. system) (A-1) with 250 DEG C of extrusion temperature, make (B1-1) with 260 DEG C of extrusion temperature, make (C-1) with 220 DEG C of extrusion temperature, make (D1-1) it is melted with 300 DEG C of extrusion temperature, collaborates the molten resin of discharge with interflow device, and be configured to stacking tubulose Body.Then, it is cooled down and is removed using the stock mould for controlling size, it is (outermost that (a) layer formed by (A-2) is made Layer), (d) layer (outer layer, innermost layer) for being formed by (D1-1), (b) layer (middle layer, internal layer 2) formed by (B1-1), by (C- 1) it when (c) layer (internal layer 1) formed, obtains layer and is configured to (a)/(d)/(b)/(c)/(b)/(d)=0.30/0.10/0.15/ And internal diameter is 6mm, outer diameter is 8mm stacking pipe 0.10/0.25/0.10mm.The physical property measurement result of the stacking pipe is shown in table 1。
Embodiment 4
In embodiment 1,12 composition of polyamide (A-1) is changed to polyamide 610 composition (A-4), by squeezing for (A-4) Temperature is changed to 260 DEG C out, in addition to this, obtains the stacking pipe of the composition of layer shown in table 1 using method same as Example 1. The physical property measurement result of the stacking pipe is shown in table 1.
Embodiment 5
In embodiment 1,12 composition of polyamide (A-1) is changed to polyamide 612 composition (A-5), by squeezing for (A-5) Temperature is changed to 260 DEG C out, in addition to this, obtains the stacking pipe of the composition of layer shown in table 1 using method same as Example 1. The physical property measurement result of the stacking pipe is shown in table 1.
Embodiment 6
In embodiment 1, polyamide 6/66/12 composition (B2-1) is changed to (B2-2), in addition to this, using with implementation The identical method of example 1 obtains the stacking pipe of the composition of layer shown in table 1.The physical property measurement result of the stacking pipe is shown in table 1.
Embodiment 7
In embodiment 1, semiaromatic polyamide composition composition (D1-1) is changed to (D1-2), by the extrusion temperature of (D1-2) 330 DEG C are changed to, in addition to this, obtains the stacking pipe of the composition of layer shown in table 1 using method same as Example 1.By the layer The physical property measurement result of folded pipe is shown in table 1.
Embodiment 8
In embodiment 1, semiaromatic polyamide composition composition (D1-1) is changed to (D1-3), by the extrusion temperature of (D1-3) 310 DEG C are changed to, in addition to this, obtains the stacking pipe of the composition of layer shown in table 1 using method same as Example 1.By the layer The physical property measurement result of folded pipe is shown in table 1.
Embodiment 9
In embodiment 2, semiaromatic polyamide composition composition (D1-1) is changed to (D1-4), by the extrusion temperature of (D1-4) 340 DEG C are changed to, in addition to this, obtains the stacking pipe of the composition of layer shown in table 1 using method same as Example 2.By the layer The physical property measurement result of folded pipe is shown in table 1.
Embodiment 10
In embodiment 2, semiaromatic polyamide composition composition (D1-1) is changed to (D1-5), by the extrusion temperature of (D1-5) 290 DEG C are changed to, in addition to this, obtains the stacking pipe of the composition of layer shown in table 1 using method same as Example 2.By the layer The physical property measurement result of folded pipe is shown in table 1.
Embodiment 11
In embodiment 2, semiaromatic polyamide composition composition (D1-1) is changed to (D1-6), by the extrusion temperature of (D1-6) 310 DEG C are changed to, in addition to this, obtains the stacking pipe of the composition of layer shown in table 1 using method same as Example 2.By the layer The physical property measurement result of folded pipe is shown in table 1.
Embodiment 12
In embodiment 1, semiaromatic polyamide composition composition (D1-1) is changed to the combination of electric conductivity semiaromatic polyamide composition The extrusion temperature of (D1-7) is changed to 310 DEG C by object (D1-7), in addition to this, obtains table using method same as Example 1 The stacking pipe that layer shown in 1 is constituted.The physical property measurement result of the stacking pipe is shown in table 1.In addition, should according to SAE J-2260 measurement It is 10 when the electric conductivity of pipe is laminated6Ω/square is hereinafter, confirm that its electrostatic removal capacity is excellent.
Embodiment 13
In embodiment 2, semiaromatic polyamide composition composition (D1-1) is changed to (D2-1), by the extrusion temperature of (D2-1) 320 DEG C are changed to, in addition to this, obtains the stacking pipe of the composition of layer shown in table 1 using method same as Example 2.By the layer The physical property measurement result of folded pipe is shown in table 1.
Embodiment 14
In embodiment 2, semiaromatic polyamide composition composition (D1-1) is changed to (D2-2), by the extrusion temperature of (D2-2) 310 DEG C are changed to, in addition to this, obtains the stacking pipe of the composition of layer shown in table 1 using method same as Example 2.By the layer The physical property measurement result of folded pipe is shown in table 1.
Embodiment 15
In embodiment 2, semiaromatic polyamide composition composition (D1-1) is changed to (D2-3), by the extrusion temperature of (D2-3) 240 DEG C are changed to, in addition to this, obtains the stacking pipe of the composition of layer shown in table 1 using method same as Example 2.By the layer The physical property measurement result of folded pipe is shown in table 1.
Embodiment 16
In embodiment 2, semiaromatic polyamide composition composition (D1-1) is changed to (D2-4), by the extrusion temperature of (D2-4) 230 DEG C are changed to, in addition to this, obtains the stacking pipe of the composition of layer shown in table 1 using method same as Example 2.By the layer The physical property measurement result of folded pipe is shown in table 1.
Embodiment 17
In embodiment 2, semiaromatic polyamide composition composition (D1-1) is changed to (D2-5), by the extrusion temperature of (D2-5) 260 DEG C are changed to, in addition to this, obtains the stacking pipe of the composition of layer shown in table 1 using method same as Example 2.By the layer The physical property measurement result of folded pipe is shown in table 1.
Embodiment 18
In embodiment 2, semiaromatic polyamide composition composition (D1-1) is changed to (D2-6), by the extrusion temperature of (D2-6) 310 DEG C are changed to, in addition to this, obtains the stacking pipe of the composition of layer shown in table 1 using method same as Example 2.By the layer The physical property measurement result of folded pipe is shown in table 1.
Embodiment 19
Use above-mentioned 12 composition of polyamide (A-1) shown, polyamide 6 composition (B1-1), polyamide 6/66/12 group Close object (B2-1), EVOH (C-1), semiaromatic polyamide composition composition (D1-1) and electric conductivity semiaromatic polyamide composition composition (D1-7), using 6 layers of pipe forming machine of Plabor (plastics engineering research institute Co. Ltd. system), squeeze (A-1) with 250 DEG C Out temperature, make (B1-1) with 260 DEG C of extrusion temperature, make (B2-1) with 260 DEG C of extrusion temperature, make (C-1) with 220 DEG C squeeze Out temperature, make (D1-1) with 300 DEG C of extrusion temperature, melt (D1-7) with 310 DEG C of extrusion temperature, made with interflow device The molten resin of discharge collaborates, and is configured to stacking tubular body.Then, cooling is carried out simultaneously using the stock mould for controlling size Removing is made (a) layer (outermost layer) formed by (A-1), (b) layer (outer layer) for being formed by (B2-1), is formed by (C-1) (c) layer (middle layer), formed by (B1-1) (b ') layer (internal layer 1), formed by (D1-1) (d) layer (internal layer 2), by (D1-7) When (the d ') layer (innermost layer) formed, obtains layer and be configured to (a)/(b)/(c)/(b ')/(d)/(d ')=0.30/0.15/0.10/ And internal diameter is 6mm, outer diameter is 8mm stacking pipe 0.25/0.10/0.10mm.The physical property measurement result of the stacking pipe is shown in table 1.It is 10 when in addition, measuring the electric conductivity of the stacking pipe according to SAE J-22606Ω/square is hereinafter, confirm that its electrostatic removes It has excellent performance.
Comparative example 1
In embodiment 1, do not use EVOH (C-1), semiaromatic polyamide composition composition (D1-1), in addition to this, using with The identical method of embodiment 1 obtains the stacking pipe of the composition of layer shown in table 1.The physical property measurement result of the stacking pipe is shown in table 1.
Comparative example 2
In embodiment 1, do not use semiaromatic polyamide composition composition (D1-1), in addition to this, utilization is same as Example 1 Method obtain layer shown in table 1 composition stacking pipe.The physical property measurement result of the stacking pipe is shown in table 1.
Comparative example 3
In embodiment 3, do not use semiaromatic polyamide composition composition (D1-1), in addition to this, utilization is same as Example 3 Method obtain layer shown in table 1 composition stacking pipe.The physical property measurement result of the stacking pipe is shown in table 1.
Comparative example 4
In embodiment 1,12 composition of polyamide (A-1), polyamide 6 composition (B1-1), polyamide 6/66/12 are not used Composition (B2-1) in addition to this obtains the stacking pipe of the composition of layer shown in table 1 using method same as Example 1.By the layer The physical property measurement result of folded pipe is shown in table 1.
Comparative example 5
In embodiment 1, polyamide 6 composition (B1-1), polyamide 6/66/12 composition (B2-1) are not used, except this it Outside, the stacking pipe of the composition of layer shown in table 1 is obtained using method same as Example 1.By the physical property measurement result of the stacking pipe It is shown in table 1.
Comparative example 6
In embodiment 2, polyamide 6/66/12 composition (B2-1) is changed to (B2-3), in addition to this, using with implementation The identical method of example 2 obtains the stacking pipe of the composition of layer shown in table 1.The physical property measurement result of the stacking pipe is shown in table 1.
Comparative example 7
In embodiment 2, polyamide 6/66/12 composition (B2-1) is changed to (B2-4), in addition to this, using with implementation The identical method of example 2 obtains the stacking pipe of the composition of layer shown in table 1.The physical property measurement result of the stacking pipe is shown in table 1.
Comparative example 8
In embodiment 2, polyamide 6/66/12 composition (B2-1) is changed to polyamide 6/12 compositions (B2-5), is removed Except this, the stacking pipe of the composition of layer shown in table 1 is obtained using method same as Example 2.By the physical property measurement of the stacking pipe As a result shown in table 1.
Comparative example 9
In embodiment 1, semiaromatic polyamide composition composition (D1-1) is changed to (D1-8), by the extrusion temperature of (D1-8) 330 DEG C are changed to, in addition to this, obtains the stacking pipe of the composition of layer shown in table 1 using method same as Example 1.By the layer The physical property measurement result of folded pipe is shown in table 1.
Comparative example 10
In embodiment 1, semiaromatic polyamide composition composition (D1-1) is changed to (D2-7), by the extrusion temperature of (D2-7) 280 DEG C are changed to, in addition to this, obtains the stacking pipe of the composition of layer shown in table 1 using method same as Example 1.By the layer The physical property measurement result of folded pipe is shown in table 1.
Comparative example 11
In embodiment 3, semiaromatic polyamide composition composition (D1-1) is changed to (D1-8), by the extrusion temperature of (D1-8) 330 DEG C are changed to, in addition to this, obtains the stacking pipe of the composition of layer shown in table 1 using method same as Example 3.By the layer The physical property measurement result of folded pipe is shown in table 1.
Comparative example 12
In embodiment 3, semiaromatic polyamide composition composition (D1-1) is changed to (D2-7), by the extrusion temperature of (D2-7) 280 DEG C are changed to, in addition to this, obtains the stacking pipe of the composition of layer shown in table 1 using method same as Example 3.By the layer The physical property measurement result of folded pipe is shown in table 1.
Comparative example 13
In embodiment 1, semiaromatic polyamide composition composition (D1-1) is changed to 12 composition of polyamide (A-2), by (A- 2) extrusion temperature is changed to 250 DEG C, in addition to this, obtains the layer of the composition of layer shown in table 1 using method same as Example 1 Folded pipe.The physical property measurement result of the stacking pipe is shown in table 1.
Comparative example 14
In embodiment 1, semiaromatic polyamide composition composition (D1-1) is changed to 12 composition (A- of Electrical Conductive Polyamide 3) extrusion temperature of (A-3), is changed to 270 DEG C, in addition to this, obtains layer shown in table 1 using method same as Example 1 The stacking pipe of composition.The physical property measurement result of the stacking pipe is shown in table 1.In addition, measuring the stacking pipe according to SAE J-2260 Electric conductivity when be 106Ω/square is hereinafter, confirm that its electrostatic removal capacity is excellent.
[table 1]
Can be defined according to table 1: without present invention provide that comprising ethylene/vinyl acetate it is saponified Layer, layer comprising semiaromatic polyamide composition composition comparative example 1 stacking pipe resistant to deterioration is fuel, anti-chemical solution penetrates Property is poor；Without present invention provide that the layer comprising semiaromatic polyamide composition composition, and have the layer conduct comprising polyamide 6 The fuel difference of resistant to deterioration of the stacking pipe of the comparative example 2 of innermost layer；Without present invention provide that include semiaromatic polyamide composition The layer of composition, and the resistant to deterioration fuel with the layer comprising polyamide 6 composition as the stacking pipe of the comparative example 3 of innermost layer Property, adhesiveness between layers are poor.Without present invention provide that the layer comprising fatty polyamide, include polyamide 6 composition, polyamides Layer after the stacking low-temperature impact resistance of pipe of the comparative example 4 of the layer of 6/66/12 composition of amine, resistant to deterioration be fuel and heat treatment Between cementability it is poor.Without present invention provide that the comparison comprising polyamide 6 composition, polyamide 6/66/12 composition layer The adhesiveness between layers of the stacking pipe of example 5 are poor.With comprising present invention provide that polyamide 6/66/12 composition, polyamide in addition Adhesiveness between layers after the heat treatment of the stacking pipe of the comparative example 6~8 of the layer of 6/12 composition are poor.With comprising present invention provide that The low-temperature impact resistance of the stacking pipe of the comparative example 9,10 of the layer of semiaromatic polyamide composition composition in addition, resistant to deterioration are fuel Difference.With comprising present invention provide that semiaromatic polyamide composition composition in addition layer comparative example 11,12 stacking pipe it is low Warm impact resistance, resistant to deterioration are fuel and adhesiveness between layers are poor.Without present invention provide that include semiaromatic polyamide composition group Close the layer of object, and with the layer comprising 12 composition of polyamide as the comparative example 13,14 of innermost layer stacking pipe to monomer, low The resistance to stripping property of polymers is poor.
On the other hand can define: present invention provide that embodiment 1~19 stacking pipe low-temperature impact resistance, resistant to deterioration combustion Each characteristic such as material property, anti-chemical solution permeability, adhesiveness between layers and its durability, resistance to monomer, oligomer stripping property is good.
Embodiment 21
Use above-mentioned 12 composition of polyamide (A-1) shown, polyamide 6 composition (B1-1), polyamide 6/66/12 group Object (B2-1), EVOH (C-1), semiaromatic polyamide composition composition (D1-1) and (E-1) containing fluorine system polymer are closed, Plabor is utilized (plastics engineering research institute Co. Ltd. system) 6 layers of pipe forming machine, make respectively (A-1) with 250 DEG C of extrusion temperature, make (B1-1) with 260 DEG C of extrusion temperature, make (B2-1) with 260 DEG C of extrusion temperature, make (C-1) with 220 DEG C of extrusion temperature, make (D1-1) with 300 DEG C of extrusion temperature melts (E-1) with 300 DEG C of extrusion temperature, closes the molten resin of discharge with interflow device Stream, and it is configured to stacking tubular body.Then, it is cooled down and is removed using the stock mould for controlling size, be made by (A-1) (a) layer (outermost layer) for being formed, (b) layer (outer layer) formed by (B2-1), (c) layer (middle layer) formed by (C-1), by (B1-1) (b ') layer (internal layer 1) for being formed, (d) layer (internal layer 2) formed by (D1-1), (e) layer formed by (E-1) are (most interior Layer) when, obtain layer be configured to (a)/(b)/(c)/(b ')/(d)/(e)=0.30/0.15/0.10/0.25/0.10/0.10mm and The stacking pipe that internal diameter is 6mm, outer diameter is 8mm.The physical property measurement result of the stacking pipe is shown in table 2.
Embodiment 22
In embodiment 21, polyamide 6 composition (B1-1) is changed to polyamide 6/66/12 composition (B2-1), removes this Except, using method identical with embodiment 21, it is made (a) layer (outermost layer) formed by (A-1), is formed by (B2-1) (b) layer (outer layer, internal layer 1), formed by (C-1) (c) layer (middle layer), formed by (D1-1) (d) layer (internal layer 2), by (E- 1) it when (e) layer (innermost layer) formed, obtains layer and is configured to (a)/(b)/(c)/(b)/(d)/(e)=0.30/0.15/0.10/ And internal diameter is 6mm, outer diameter is 8mm stacking pipe 0.25/0.10/0.10mm.The physical property measurement result of the stacking pipe is shown in table 2。
Embodiment 23
In embodiment 21,12 composition of polyamide (A-1) is changed to (A-2), does not use polyamide 6/66/12 composition (B2-1), in addition to this, using method identical with embodiment 21, be made (a) layer (outermost layer) formed by (A-1), by (D1-1) (d) layer (outer layer) for being formed, formed by (B1-1) (b) layer (middle layer, internal layer 2), (c) layer for being formed by (C-1) When (internal layer 1), (e) layer (innermost layer) formed by (E-1), obtain layer be configured to (a)/(d)/(b)/(c)/(b)/(e)= And internal diameter is 6mm, outer diameter is 8mm stacking pipe 0.30/0.10/0.15/0.10/0.25/0.10mm.By the physical property of the stacking pipe Measurement result is shown in table 2.
Embodiment 24
In embodiment 23,12 composition of polyamide (A-2) is changed to polyamide 610 composition (A-4), by (A-4) Extrusion temperature is changed to 260 DEG C, in addition to this, obtains the stacking of the composition of layer shown in table 2 using method identical with embodiment 23 Pipe.The physical property measurement result of the stacking pipe is shown in table 2.
Embodiment 25
In embodiment 23,12 composition of polyamide (A-2) is changed to polyamide 612 composition (A-5), by (A-5) Extrusion temperature is changed to 260 DEG C, in addition to this, obtains the stacking of the composition of layer shown in table 2 using method identical with embodiment 23 Pipe.The physical property measurement result of the stacking pipe is shown in table 2.
Embodiment 26
In embodiment 21, polyamide 6/66/12 composition (B2-1) is changed to (B2-2), in addition to this, using with reality It applies the identical method of example 21 and obtains the stacking pipe of the composition of layer shown in table 2.The physical property measurement result of the stacking pipe is shown in table 2.
Embodiment 27
In embodiment 21, semiaromatic polyamide composition composition (D1-1) is changed to (D1-2), by the extrusion temperature of (D1-2) Degree is changed to 330 DEG C, in addition to this, obtains the stacking pipe of the composition of layer shown in table 2 using method identical with embodiment 21.It should The physical property measurement result of stacking pipe is shown in table 2.
Embodiment 28
In embodiment 21, semiaromatic polyamide composition composition (D1-1) is changed to (D1-3), by the extrusion temperature of (D1-3) Degree is changed to 310 DEG C, in addition to this, obtains the stacking pipe of the composition of layer shown in table 2 using method identical with embodiment 21.It should The physical property measurement result of stacking pipe is shown in table 2.
Embodiment 29
In embodiment 22, semiaromatic polyamide composition composition (D1-1) is changed to (D1-4), by the extrusion temperature of (D1-4) Degree is changed to 340 DEG C, in addition to this, obtains the stacking pipe of the composition of layer shown in table 2 using method identical with embodiment 22.It should The physical property measurement result of stacking pipe is shown in table 2.
Embodiment 30
In embodiment 22, semiaromatic polyamide composition composition (D1-1) is changed to (D1-5), by the extrusion temperature of (D1-5) Degree is changed to 290 DEG C, in addition to this, obtains the stacking pipe of the composition of layer shown in table 2 using method identical with embodiment 22.It should The physical property measurement result of stacking pipe is shown in table 2.
Embodiment 31
In embodiment 22, semiaromatic polyamide composition composition (D1-1) is changed to (D1-6), by the extrusion temperature of (D1-6) Degree is changed to 310 DEG C, in addition to this, obtains the stacking pipe of the composition of layer shown in table 2 using method identical with embodiment 22.It should The physical property measurement result of stacking pipe is shown in table 2.
Embodiment 32
In embodiment 22, semiaromatic polyamide composition composition (D1-1) is changed to (D2-1), by the extrusion temperature of (D2-1) Degree is changed to 320 DEG C, in addition to this, obtains the stacking pipe of the composition of layer shown in table 2 using method identical with embodiment 22.It should The physical property measurement result of stacking pipe is shown in table 2.
Embodiment 33
In embodiment 22, semiaromatic polyamide composition composition (D1-1) is changed to (D2-2), by the extrusion temperature of (D2-2) Degree is changed to 310 DEG C, in addition to this, obtains the stacking pipe of the composition of layer shown in table 2 using method identical with embodiment 22.It should The physical property measurement result of stacking pipe is shown in table 2.
Embodiment 34
In embodiment 22, semiaromatic polyamide composition composition (D1-1) is changed to (D2-3), by the extrusion temperature of (D2-3) Degree is changed to 240 DEG C, in addition to this, using method identical with embodiment 22, obtains the stacking pipe of the composition of layer shown in table 2.It will The physical property measurement result of the stacking pipe is shown in table 2.
Embodiment 35
In embodiment 22, semiaromatic polyamide composition composition (D1-1) is changed to (D2-4), by the extrusion temperature of (D2-4) Degree is changed to 230 DEG C, in addition to this, obtains the stacking pipe of the composition of layer shown in table 2 using method identical with embodiment 22.It should The physical property measurement result of stacking pipe is shown in table 2.
Embodiment 36
In embodiment 22, semiaromatic polyamide composition composition (D1-1) is changed to (D2-5), by the extrusion temperature of (D2-5) Degree is changed to 260 DEG C, in addition to this, obtains the stacking pipe of the composition of layer shown in table 2 using method identical with embodiment 22.It should The physical property measurement result of stacking pipe is shown in table 2.
Embodiment 37
In embodiment 22, semiaromatic polyamide composition composition (D1-1) is changed to (D2-6), by the extrusion temperature of (D2-6) Degree is changed to 310 DEG C, in addition to this, obtains the stacking pipe of the composition of layer shown in table 2 using method identical with embodiment 22.It should The physical property measurement result of stacking pipe is shown in table 2.
Embodiment 38
In embodiment 21, fluorine system polymer (E-1) will be contained and be changed to electric conductivity (E-2) containing fluorine system polymer, by (E-2) Extrusion temperature is changed to 310 DEG C, in addition to this, obtains the stacking of the composition of layer shown in table 2 using method identical with embodiment 21 Pipe.The physical property measurement result of the stacking pipe is shown in table 2.In addition, when measuring the electric conductivity of the stacking pipe according to SAE J-2260 It is 106Ω/square is hereinafter, confirm that its electrostatic removal capacity is excellent.
Embodiment 39
In embodiment 21, fluorine system polymer (E-1) will be contained and be changed to (E-5), the extrusion temperature of (E-5) is changed to 310 DEG C, in addition to this, the stacking pipe of the composition of layer shown in table 2 is obtained using method identical with embodiment 21.By the object of the stacking pipe Property measurement result is shown in table 2.
Embodiment 40
In embodiment 21, fluorine system polymer (E-1) will be contained and be changed to electric conductivity (E-6) containing fluorine system polymer, by (E-6) Extrusion temperature is changed to 320 DEG C, in addition to this, obtains the stacking of the composition of layer shown in table 2 using method identical with embodiment 21 Pipe.The physical property measurement result of the stacking pipe is shown in table 2.In addition, when measuring the electric conductivity of the stacking pipe according to SAE J-2260 It is 106Ω/square is hereinafter, confirm that its electrostatic removal capacity is excellent.
Embodiment 41
In embodiment 21, fluorine system polymer (E-1) will be contained and be changed to (E-8), the extrusion temperature of (E-8) is changed to 290 DEG C, in addition to this, the stacking pipe of the composition of layer shown in table 2 is obtained using method identical with embodiment 21.By the object of the stacking pipe Property measurement result is shown in table 2.
Embodiment 42
In embodiment 21, fluorine system polymer (E-1) will be contained and be changed to electric conductivity (E-9) containing fluorine system polymer, in addition to this, The stacking pipe of the composition of layer shown in table 2 is obtained using method identical with embodiment 21.The physical property measurement result of the stacking pipe is shown In table 2.It is 10 when in addition, measuring the electric conductivity of the stacking pipe according to SAE J-22606Ω/square is hereinafter, confirm its electrostatic Removal capacity is excellent.
Comparative example 21
In embodiment 21, EVOH (C-1), semiaromatic polyamide composition composition (D1-1), (E- containing fluorine system polymer are not used 1), in addition to this, the stacking pipe of the composition of layer shown in table 2 is obtained using method identical with embodiment 21.By the object of the stacking pipe Property measurement result is shown in table 2.
Comparative example 22
In embodiment 23, do not use semiaromatic polyamide composition composition (D1-1), in addition to this, using with 23 phase of embodiment Same method obtains the stacking pipe of the composition of layer shown in table 2.The physical property measurement result of the stacking pipe is shown in table 2.
Comparative example 23
In embodiment 23,12 composition of polyamide (A-2), polyamide 6 composition (B1-1) are not used, in addition to this, benefit The stacking pipe of the composition of layer shown in table 2 is obtained with method identical with embodiment 23.The physical property measurement result of the stacking pipe is shown in Table 2.
Comparative example 24
In embodiment 21, polyamide 6 composition (B1-1), polyamide 6/66/12 composition (B2-1) are not used, except this it Outside, the stacking pipe of the composition of layer shown in table 2 is obtained using method identical with embodiment 21.By the physical property measurement result of the stacking pipe It is shown in table 2.
Comparative example 25
In embodiment 22, polyamide 6/66/12 composition (B2-1) is changed to (B2-3), in addition to this, using with reality It applies the identical method of example 22 and obtains the stacking pipe of the composition of layer shown in table 2.The physical property measurement result of the stacking pipe is shown in table 2.
Comparative example 26
In embodiment 22, polyamide 6/66/12 composition (B2-1) is changed to (B2-4), in addition to this, using with reality It applies the identical method of example 22 and obtains the stacking pipe of the composition of layer shown in table 2.The physical property measurement result of the stacking pipe is shown in table 2.
Comparative example 27
In embodiment 22, polyamide 6/66/12 composition (B2-1) is changed to polyamide 6/12 compositions (B2-5), is removed Except this, the stacking pipe of the composition of layer shown in table 2 is obtained using method identical with embodiment 22.By the physical property measurement of the stacking pipe As a result it is shown in table 2.
Comparative example 28
In embodiment 23, semiaromatic polyamide composition composition (D1-1) is changed to (D1-8), by the extrusion temperature of (D1-8) Degree is changed to 330 DEG C, in addition to this, obtains the stacking pipe of the composition of layer shown in table 2 using method identical with embodiment 23.It should The physical property measurement result of stacking pipe is shown in table 2.
Comparative example 29
In embodiment 23, semiaromatic polyamide composition composition (D1-1) is changed to (D2-7), by the extrusion temperature of (D2-7) Degree is changed to 280 DEG C, in addition to this, obtains the stacking pipe of the composition of layer shown in table 2 using method identical with embodiment 23.It should The physical property measurement result of stacking pipe is shown in table 2.
Comparative example 30
In embodiment 21, fluorine system polymer (E-1) will be contained and be changed to (E-3), in addition to this, using identical as embodiment 21 Method obtain layer shown in table 2 composition stacking pipe.The physical property measurement result of the stacking pipe is shown in table 2.
Comparative example 31
In embodiment 21, fluorine system polymer (E-1) will be contained and be changed to electric conductivity (E-4) containing fluorine system polymer, by (E-4) Extrusion temperature is changed to 310 DEG C, in addition to this, obtains the stacking of the composition of layer shown in table 2 using method identical with embodiment 21 Pipe.The physical property measurement result of the stacking pipe is shown in table 2.In addition, when measuring the electric conductivity of the stacking pipe according to SAE J-2260 It is 106Ω/square is hereinafter, confirm that its electrostatic removal capacity is excellent.
Comparative example 32
In embodiment 21, fluorine system polymer (E-1) will be contained and be changed to (E-7), the extrusion temperature of (E-7) is changed to 310 DEG C, in addition to this, the stacking pipe of the composition of layer shown in table 2 is obtained using method identical with embodiment 21.By the object of the stacking pipe Property measurement result is shown in table 2.
Comparative example 33
In embodiment 21, fluorine system polymer (E-1) will be contained and be changed to (E-10), in addition to this, using with 21 phase of embodiment Same method obtains the stacking pipe of the composition of layer shown in table 2.The physical property measurement result of the stacking pipe is shown in table 2.
Comparative example 34
In embodiment 21, fluorine system polymer (E-1) will be contained and be changed to 12 composition of polyamide (A-2), by the extrusion of (A-2) Temperature is changed to 250 DEG C, in addition to this, obtains the stacking pipe of the composition of layer shown in table 2 using method identical with embodiment 21.It will The physical property measurement result of the stacking pipe is shown in table 2.
Comparative example 35
In embodiment 21, fluorine system polymer (E-2) will be contained and be changed to 12 composition of Electrical Conductive Polyamide (A-3), by (A-3) Extrusion temperature be changed to 270 DEG C, in addition to this, using method identical with embodiment 21 obtain layer shown in table 2 composition layer Folded pipe.The physical property measurement result of the stacking pipe is shown in table 2.In addition, measuring the electric conductivity of the stacking pipe according to SAE J-2260 When, it is 106Ω/square is hereinafter, confirm that its electrostatic removal capacity is excellent.
[table 2]
Can be defined according to table 2: without present invention provide that comprising ethylene/vinyl acetate it is saponified Layer, the layer comprising semiaromatic polyamide composition composition and the comparative example 21 comprising the layer containing fluorine system polymer stacking pipe it is resistance to bad The anti-permeability for changing gasoline fuel, to the alcohol containing high concentration is poor；Without present invention provide that include semiaromatic polyamide composition The adhesiveness between layers of the stacking pipe of the comparative example 22 of the layer of composition are poor.Without present invention provide that include fatty polyamide Layer, comprising polyamide 6 composition, polyamide 6/66/12 composition layer comparative example 23 stacking pipe low temperature impact Property, resistant to deterioration is fuel and adhesiveness between layers are poor.Without present invention provide that include polyamide 6 composition, polyamide 6/66/ The adhesiveness between layers of the stacking pipe of the comparative example 24 of the layer of 12 compositions are poor.With comprising present invention provide that polyamide 6 in addition/ Adhesiveness between layers after the heat treatment of the stacking pipe of the comparative example 25~27 of 66/12 composition, polyamide 6/12 compositions layer Difference.With comprising present invention provide that semiaromatic polyamide composition composition in addition layer comparative example 28,29 stacking pipe layer Between cementability it is poor.With comprising present invention provide that the layer containing fluorine system polymer in addition comparative example 30~33 stacking pipe layer Between cementability it is poor.Without present invention provide that include the layer containing fluorine system polymer, and have include 12 composition of polyamide Layer is as the gasoline permeability of the anti-alcohol containing high concentration of the stacking pipe of the comparative example 34,35 of innermost layer, resistance to monomer, oligomer dissolution Property is poor.
On the other hand can define: present invention provide that the stacking low-temperature impact resistance of pipe of embodiment 21~42, resistant to deterioration Fuel, anti-chemical solution permeability, the especially anti-alcohol containing high concentration gasoline permeability, adhesiveness between layers and its durability, Each characteristics such as resistance to monomer, oligomer stripping property are good.
By Japanese patent application No. 2014-185784 (applying date: on September 12nd, 2014), Japanese patent application 2014- The complete disclosure of No. 185787 (applying date: on September 12nd, 2014) is used as reference to quote into this specification.
All documents, patent application and the technical standard that this specification is recorded are quoted as reference into this specification, With by referring to and quote each document, patent application and technical standard and specific and the case where record respectively degree is identical.

Claims (23)

1. a kind of stacking pipe, is the stacking pipe for having (a) layer, (b) layer, (c) layer and (d) layer and at least being formed by 4 layers,
(a) layer includes fatty polyamide (A),
(b) layer includes polyamide 6 composition (B1) and/or polyamide 6/66/12 composition (B2),
(c) layer includes that ethylene/vinyl acetate is saponified (C),
(d) layer includes semiaromatic polyamide composition composition D1 or semiaromatic polyamide composition composition D2,
The fatty polyamide (A) is free of polycaprolactam (polyamide 6) and poly- (caproamide/hexamethylene adipamide/dodecanoyl Amine) (polyamide 6/66/12),
The polyamide 6 composition (B1) contains polycaprolactam (polyamide 6) 50 mass % or more and 98 mass % or less, plasticising 1 mass % of agent B3 or more and 20 mass % or less and according to ISO 178 measure bending elastic modulus be 500MPa or less 1 mass % of olefin polymer B4 or more and 30 mass % hereinafter,
The polyamide 6/66/12 composition (B2) contains 50 mass % of polyamide compound or more and 98 mass % or less, increasing Mould 1 mass % of agent B3 or more and 20 mass % or less and according to the bending elastic modulus that ISO 178 is measured be 500MPa with Under 1 mass % of olefin polymer B4 or more and 30 mass % hereinafter, the polyamide compound include polyamide 6/66/12 With selected from by polyhexamethylene sebacamide (polyamide 610), nylon 612 (polyamide 612), poly- decanedioyl nonyl two Amine (polyamide 910), two acyl nonamethylene diamine (polyamide 912) of poly- dodecane, nylon 1010 (polyamide 1010), poly- 12 It is at least one kind of poly- in the group of two acyl decamethylene diamine (polyamide 1012) of alkane and two acyl lauryl amine (polyamide 1212) of poly- dodecane composition Amide,
The semiaromatic polyamide composition composition D1 includes semiaromatic polyamide composition d1, and the semiaromatic polyamide composition d1 has two Amine unit and dicarboxylic acid units, the diamine unit include relative to whole diamine units be 50 moles of % or more, carbon number 9 with Upper and 13 aliphatic diamine units below, the dicarboxylic acid units include relative to whole dicarboxylic acid units be 50 moles of % with On terephthalic acid units and/or naphthalenedicarboxylic acid unit,
The semiaromatic polyamide composition composition D2 includes semiaromatic polyamide composition d2, and the semiaromatic polyamide composition d2 has two Amine unit and dicarboxylic acid units, the diamine unit include the benzene dimethylamine for being 50 moles of % or more relative to whole diamine units Unit and/or bis- (amino methyl) naphthalene units, it is 50 moles of % that the dicarboxylic acid units, which include relative to whole dicarboxylic acid units, Above, the aliphatic dicarboxylic acid unit below of carbon number 8 or more and 13,
(d) layer is configured in innermost layer, and (c) layer is configured between described (a) layer and (d) layer, with institute State (b) layer described in the adjacent at least side configuration of (c) layer.
2. stacking pipe according to claim 1, wherein the fatty polyamide (A) is selected from by poly- undecanoic amide (polyamide 11), poly- dodecane amide (polyamide 12), polyhexamethylene adipamide (polyamide 66), polyhexamethylene sebacamide are (poly- Amide 610), nylon 612 (polyamide 612), nylon 1010 (polyamide 1010), poly- dodecane two At least one kind of homopolymerization in the group of acyl decamethylene diamine (polyamide 1012) and two acyl lauryl amine (polyamide 1212) of poly- dodecane composition Copolymer obtained from object, and/or a variety of starting monomers for forming these polyamide of use.
3. stacking pipe according to claim 1 or 2, wherein the polyamide in the polyamide 6/66/12 composition (B2) In 6/66/12, add up to 100 mass % relative to hexanoyl amine unit, hexamethyleneadipamide unit and dodecanoyl amine unit, oneself The mass ratio of the total unit of amide units and hexamethyleneadipamide unit and dodecanoyl amine unit is 81 mass %:19 matter Measure % or more and 95 mass %:5 mass % or less.
4. stacking pipe according to claim 1 or 2, wherein the ethylene/vinyl acetate saponified (C) Ethylene contents are 15 moles of % or more and 60 mole of % hereinafter, saponification degree is 90 moles of % or more.
5. stacking pipe according to claim 1 or 2, wherein (a) layer is configured in outermost layer.
6. stacking pipe according to claim 1 or 2, wherein (d) layer is further containing the conduction of electroconductive stuffing Layer is configured in the innermost layer of the stacking pipe.
7. a kind of stacking pipe, is the stacking for having (a) layer, (b) layer, (c) layer, (d) layer and (e) layer and at least being formed by 5 layers Pipe,
(a) layer includes fatty polyamide (A),
(b) layer includes polyamide 6 composition (B1) and/or polyamide 6/66/12 composition (B2),
(c) layer includes that ethylene/vinyl acetate is saponified (C),
(d) layer includes semiaromatic polyamide composition composition D1 or semiaromatic polyamide composition composition D2,
(e) layer includes (E) containing fluorine system polymer, and (E) containing fluorine system polymer has been imported in strand has amino There is reactive functional group,
The fatty polyamide (A) is free of polycaprolactam (polyamide 6) and poly- (caproamide/hexamethylene adipamide/dodecanoyl Amine) (polyamide 6/66/12),
The polyamide 6 composition (B1) contains polycaprolactam (polyamide 6) 50 mass % or more and 98 mass % or less, plasticising 1 mass % of agent B3 or more and 20 mass % or less and according to ISO 178 measure bending elastic modulus be 500MPa or less 1 mass % of olefin polymer B4 or more and 30 mass % hereinafter,
The polyamide 6/66/12 composition (B2) contains 50 mass % of polyamide compound or more and 98 mass % or less, increasing Mould 1 mass % of agent B3 or more and 20 mass % or less and according to the bending elastic modulus that ISO 178 is measured be 500MPa with Under 1 mass % of olefin polymer B4 or more and 30 mass % hereinafter, the polyamide compound include polyamide 6/66/12 With selected from by polyhexamethylene sebacamide (polyamide 610), nylon 612 (polyamide 612), poly- decanedioyl nonyl two Amine (polyamide 910), two acyl nonamethylene diamine (polyamide 912) of poly- dodecane, nylon 1010 (polyamide 1010), poly- 12 It is at least one kind of poly- in the group of two acyl decamethylene diamine (polyamide 1012) of alkane and two acyl lauryl amine (polyamide 1212) of poly- dodecane composition Amide,
The semiaromatic polyamide composition composition D1 includes semiaromatic polyamide composition d1, and the semiaromatic polyamide composition d1 has two Amine unit and dicarboxylic acid units, the diamine unit include relative to whole diamine units be 50 moles of % or more, carbon number 9 with Upper and 13 aliphatic diamine units below, the dicarboxylic acid units include relative to whole dicarboxylic acid units be 50 moles of % with On terephthalic acid units and/or naphthalenedicarboxylic acid unit,
The semiaromatic polyamide composition composition D2 includes semiaromatic polyamide composition d2, and the semiaromatic polyamide composition d2 has two Amine unit and dicarboxylic acid units, the diamine unit include the benzene dimethylamine for being 50 moles of % or more relative to whole diamine units Unit and/or bis- (amino methyl) naphthalene units, it is 50 moles of % that the dicarboxylic acid units, which include relative to whole dicarboxylic acid units, Above, the aliphatic dicarboxylic acid unit below of carbon number 8 or more and 13,
(e) layer is configured in innermost layer, and (c) layer and (d) layer are configured in described (a) layer and described (e) Between layer, (b) layer described in at least side configuration adjacent with (c) layer.
8. stacking pipe according to claim 7, wherein (a) layer is configured in outermost layer.
9. stacking pipe according to claim 7 or 8, wherein (e) layer is further containing the conduction of electroconductive stuffing Layer is configured in the innermost layer of the stacking pipe.
10. according to claim 1, stacking pipe described in 2,7 or 8 is manufactured by coextrusion forming process.
11. stacking pipe according to claim 3, is manufactured by coextrusion forming process.
12. stacking pipe according to claim 4, is manufactured by coextrusion forming process.
13. stacking pipe according to claim 5, is manufactured by coextrusion forming process.
14. stacking pipe according to claim 6, is manufactured by coextrusion forming process.
15. stacking pipe according to claim 9, is manufactured by coextrusion forming process.
16. according to claim 1, stacking pipe described in 2,7 or 8, is used as cartridge.
17. stacking pipe according to claim 3, is used as cartridge.
18. stacking pipe according to claim 4, is used as cartridge.
19. stacking pipe according to claim 5, is used as cartridge.
20. stacking pipe according to claim 6, is used as cartridge.
21. stacking pipe according to claim 9, is used as cartridge.
22. the manufacturing method of stacking pipe according to any one of claims 1 to 9 comprising carry out coextrusion forming.
23. the purposes as cartridge of stacking pipe according to any one of claims 1 to 9.
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